KR101685266B1

KR101685266B1 - Fluorine-containing copolymer, and oil- and/or water-repellent coating agent

Info

Publication number: KR101685266B1
Application number: KR1020147024372A
Authority: KR
Inventors: 도모미 이리타; 다카부미 나가이; 겐지 아다치; 요시토 다나카; 가케루 하나부사; 에이지 사카모토; 도모히로 요시다; 사야 요코타니; 사다히토 아오시마; 쇼쿄쿠 가나오카
Original assignee: 다이킨 고교 가부시키가이샤; 고꾸리쯔 다이가꾸 호우징 오사까 다이가꾸
Priority date: 2012-02-01
Filing date: 2013-02-01
Publication date: 2016-12-09
Also published as: WO2013115380A1; TW201348269A; KR20140122262A; JPWO2013115380A1; JP5840236B2; TWI565719B; CN104203998B; CN104203998A

Abstract

It is an object of the present invention to provide a fluorine-containing copolymer having excellent oil repellency and high solubility in a general solvent (fluorine-free organic solvent), and a oil repellent and / or water repellent coating agent containing the same. The present invention relates to compounds of formula (1)

^Wherein R ^a1 , R ^a2 , R ^a3 , X ^a , X ^c , Q, R ^c , k and n1 are as described in the specification.

Description

FLUORINE-CONTAINING COPOLYMER, AND OIL-AND / OR WATER-REPELLENT COATING AGENT)

The present invention relates to a fluorine-containing copolymer, particularly a fluorine-containing copolymer containing a curable part, and an oil-repellent and / or water-repellent coating agent containing the fluorine-containing copolymer.

2. Description of the Related Art Conventionally, a device such as a touch panel, which is operated by touching the surface of a display device with a finger, is used. The surface of such a display device is usually made of a material such as glass or amorphous synthetic resin (e.g., acrylic resin). However, since such a material does not have oil repellency, there is a problem that the retention of the finger is adhered to the surface of the display device, thereby lowering the visibility of the display.

For this reason, fluorine-containing compounds having excellent oil repellency, particularly fluorine-containing compounds containing perfluoropolyether groups, have been used as oil repellent coatings on display surfaces for the purpose of preventing adhesion of the surfaces (Patent Documents 1 to 3).

Since such a fluorine-containing compound has low solubility in a general-purpose solvent (fluorine-free organic solvent), it is necessary to dissolve it in an expensive fluorine-containing organic solvent when it is applied to a display surface.

However, in recent years, due to the spread of the tablet or the slate computer, the area of the display surface to be operated by touching with the fingers becomes larger, and the amount of the fluorine-containing compound and the expensive fluorine-

Therefore, there is a demand for a fluorine-containing compound which does not contain fluorine and has high solubility in an inexpensive general-purpose solvent.

Further, in order to form a film which is hardly peeled off from the surface of various substrates, for example, there is a method of obtaining a surface coating film by polymerizing an acrylic monomer as in the case of a conventional acrylic hard coating agent. This method is versatile as a surface modification method. That is, when a fluorine-containing compound containing a perfluoropolyether group which is compatible with and copolymerizable with an acrylic hard coating agent is prepared, a surface modifying agent suitable for various substrates can be obtained by combining the fluorine-containing compound and the acrylic hard coating agent , And the physical properties of the resulting polymer film can be changed. Further, since the conventional acrylic monomer is used as the main component of the coating film, the amount of the fluorine-containing compound containing an expensive perfluoropolyether group can be reduced, which is advantageous in terms of cost.

Also from this, a fluorine-containing compound which is compatible with an acrylic hard coating agent and contains a perfluoropolyether group copolymerizable by a curable site is useful.

As the fluorine-containing compound containing a perfluoropolyether group and a curable part, for example, the following are known.

Patent Document 4 relates to a protective coating, wherein an ethyl isocyanate-methacrylate-modified product of perfluoropolyether having a hydroxyl group at the end thereof is added to bisphenol A-dihydroxyethyl acrylate and copolymerized to fix (Patent Document 4, Examples 5 and 10).

Non-Patent Document 1 discloses a copolymer of methyl isocyanate-methacrylate-modified product of perfluoropolyether having a hydroxyl group at the terminal thereof and methyl methacrylate.

Patent Document 5 discloses a method for introducing an addition polymerizable group having an active hydroxyl group for the purpose of modifying a crosslinking forming functional group on an oligourethane having a perfluoropolyether segment.

Japanese Patent Laid-Open No. 9-157582 Japanese Patent Application Laid-Open No. 9-157388 International Publication No. 2003/002628 pamphlet Japanese Unexamined Patent Application Publication No. 10-72568 Japanese Patent Application Laid-Open No. 2001-19736

Polymer, 42, 2001, pp.2299-2305

As described above, the conventional fluorine-containing compounds having excellent oil repellency have low solubility in general-purpose solvents (fluorine-free organic solvents), while the conventional fluorine-containing compounds having high solubility in general- There was a problem that it was low.

In addition, in the technique proposed in Patent Document 4, only up to 1% by weight of the perfluoropolyether is added. Since the methacrylic hydrocarbon group portion of the ethyl isocyanate-methacrylate-modified perfluoropolyether is smaller than the fluoroalkyl group portion, the fluorine-containing compound of Patent Document 4 tends to be repelled from the base material, Acrylate monomers and hydrocarbon-based solvents. This is because the types of monomers that can be used for commercialization are limited and they can not be added to a coating agent having a composition optimized for each application and that the addition of a high concentration makes it difficult for a solution before curing to be phase separated to obtain a uniform film . In addition, when the composition is used for a transparent protective layer used for optical use, it is necessary to make the protective film thin, and at this time, the surface modification effect is hard to appear unless added at a relatively high concentration.

In the copolymer of Non-Patent Document 1, since the ethyl isocyanate-methacrylate-modified product of perfluoropolyether does not dissolve in the hydrocarbon-based solvent, the specific freon, 1,1,2-trichlorotrifluoroethane , Or expensive fluorine solvents such as expensive trifluoro toluene. Further, in the non-fluorine-based medium, since the film can be formed only in the form of a copolymer, the flexibility of the film properties is insufficient. Therefore, there is a limitation in the substrate on which the copolymer can be coated. In addition, since it can not be added to a coating agent only in the form of a copolymer, there is a limit to a coating agent that can be used for commercialization, and it is difficult to obtain a strong and uniform film.

In the technique proposed in Patent Document 5, the main component of the surface protective coating is an oligourethane (perfluoropolyether-containing urethane crosslinked product), and there are physical limitations such as being unsuitable for applications requiring hardness. This method does not add a protective coating to an existing addition-polymerizable coating agent.

Accordingly, the present invention provides a fluorine-containing copolymer which has excellent oil repellency and / or water repellency and high solubility in a general solvent (fluorine-free organic solvent) and which can be used in addition to existing hard coating agents, And / or a water repellent coating agent which is a water-repellent coating agent.

As a result of intensive studies, the inventors of the present invention have found that when the formula (1)

[Wherein,

R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group. k represents 1 or 2;

X ^a represents -O-, phenylene, -N (-R ^E ) - (wherein R ^E represents an organic group), or carbazolylene.

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

Q represents a constituent unit containing a curable component or a constituent unit not containing a curable component in each occurrence independently of each other.

R ^c represents a group containing a perfluoropolyether group or an organic group which may contain a curable part or a hydrogen atom.

X ^c represents -O-, -S-, -NH-, or a single bond.

n1 represents one or more repeating numbers.

Provided that at least one of R ^a2 and R ^a3 is an alkyl group,

When R ^c is not an organic group containing a curable component, at least one Q is a structural unit containing a curable component.]

(Fluorine-containing organic solvent) has excellent oil and water repellency and high solubility in a general solvent (fluorine-free organic solvent), thereby completing the present invention.

That is, the present invention includes the following modes.

Section 1.

Equation (1):

[Wherein,

R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group.

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

X ^c represents -O-, -S-, -NH-, or a single bond.

k represents 1 or 2;

n1 represents one or more repeating numbers.

Provided that at least one of R ^a2 and R ^a3 is an alkyl group.

The fluorine-containing copolymer

Section 2.

Q is a formula:

[Wherein,

Each occurrence of R ^b1 in each occurrence represents a hydrogen atom or an alkyl group.

R ^b2 represents, independently at each occurrence, an organic group which may contain a hydrogen atom or a curable part.

R ^b3 represents a hydrogen atom or an alkyl group.

X ^b represents -O-, phenylene, -N (-R ^E ) - (wherein R ^E represents an organic group), or carbazolylene.

Provided that when R ^b2 is a hydrogen atom, X ^b is phenylene.

Is a structural unit represented by the following formula (1).

Section 3.

The fluorine-containing copolymer according to item 1 or 2, wherein the number average molecular weight of the perfluoropolyether group in the monovalent or divalent group containing a perfluoropolyether group represented by R ^a1 is about 1000 or more.

Section 4.

The perfluoropolyether group in the group containing a perfluoropolyether group represented by R ^a1 is a group represented by the formula: - (C _p F _2p O) _n -

[Wherein,

p is, independently at each occurrence, an integer of 1 to 6 in each occurrence.

n represents the number of repeats]

Containing copolymer according to any one of < RTI ID = 0.0 > 1 to 3. < / RTI >

Item 5.

R < ^a1 &

Formula: X ^ra - (C _p F _2p O) _na -Y ^ra -L ^a - (a1)

[Wherein,

X ^ra represents fluorine or R f -O- (R f represents a perfluoroalkyl group having 1 to 8 carbon atoms).

p represents, independently for each occurrence, an integer of 1 to 6;

and na represents the number of repeats from 1 to 1000.

Y ^ra represents a perfluoro alkylene chain having 1 to 6 carbon atoms.

L ^a represents a linker]

Is a monovalent group represented by the following formula (1).

Section 6.

The moiety represented by the formula (C _p F _2p O) _na in the formula (a1) is -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O-, -CF ₂ -O-, -CF ₂ -CF ₂ -O-, and -CF (-CF ₃₎ a fluorine-containing copolymer according to item 5, comprising a structural unit at least one selected from the group consisting of -O-.

Item 7.

The moiety represented by the formula: (C _p F _2p O) _na contains -CF ₂ -CF ₂ -CF ₂ -O-,

Y is ^ra, -CF ₂ -CF ₂ - wherein the fluorine-containing copolymer according to item 6.

Section 8.

The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -CF ₂ -O- and -CF ₂ -O-,

The fluorine-containing copolymer according to item 6, wherein Y ^ra is -CF ₂ -.

Section 9.

Formula: (CpF _2p O) portion is represented by _na, -CF include (-CF ₃₎ -CF ₂ -O-, and also

Y is ^ra, -CF (-CF ₃₎ - a fluorine-containing copolymer according to item 6, wherein.

Item 10.

The moiety represented by the formula: (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O- and -CF ₂ -O-,

Section 11.

L ^a is -CH ₂ -O-CH ₂ -CH ₂ -.

Item 12.

The fluorine-containing copolymer according to any one of items 5 to 10, wherein L ^a is -CH ₂ -.

Item 13.

R < ^a1 &

^???????? - L ^{a '} -Y ^ra' -O- (C _p F _2p O) _na -Y ^ra -L ^a - (a2)

[Wherein,

L ^{a '} and L ^a independently represent a linker.

Y ^{ra '} and Y ^ra each independently represent a perfluoroalkylene chain having 1 to 6 carbon atoms.

p represents, independently for each occurrence, an integer of 1 to 6;

na represents the number of repeats from 1 to 1000;

Is a divalent group represented by the following formula (1).

Item 14.

The moiety represented by the formula (C _p F _2p O) _na in the formula (a2) is independently selected from -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O _{-, -CF 2 -O-, -CF 2} -CF 2 -O-, and the fluorine-containing air according to -CF (-CF ₃₎ -O-, wherein comprising a structural unit at least one member selected from the group consisting of 13 coalescence.

Item 15.

Y ^{ra '} is -CF ₂ -CF ₂ -

The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -CF ₂ -CF ₂ -O-,

The fluorine-containing copolymer according to item 13, wherein Y ^ra is -CF ₂ -CF ₂ -.

Item 16.

Y ^{ra '} is -CF ₂ -

The fluorine-containing copolymer according to item 13, wherein ^Yra is -CF ₂ -.

Item 17.

Y ^{ra '} is -CF (-CF ₃ ) -,

The moiety represented by the formula: (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O-,

Y is ^ra, -CF (-CF ₃₎ -, wherein the fluorine-containing copolymer according to item 13.

Item 18.

Y ^{ra '} is -CF (-CF ₃ ) -,

Item 19.

The perfluoropolyether group in the group containing a perfluoropolyether group represented by R < ^a1 &^gt;

^{Formula: -L a '-Y ra' -} (OC p 'F 2p') na '-O-Rf-O- (C p F 2p O) na -Y ra -L a - (a2')

[Wherein,

L ^{a '} and L ^a independently represent a linker.

na ' and na each independently represent a repeating number of 1 to 1000.

And Rf represents a perfluoroalkylene chain.

Is a divalent group represented by the following formula (1).

Section 20.

Y ^{ra 'is,} -CF (-CF ₃₎ - is;

The moiety represented by the formula: (OC _{p '} F _2p' ) _{na '} includes -O-CF ₂ -CF (-CF ₃ ) -;

Rf is a perfluoroalkylene chain having 1 to 8 carbon atoms;

The moiety represented by the formula: (C _p F _2p O) _na is -CF (-CF ₃ ) -CF ₂ -O-; Also

Y is ^ra, -CF (-CF ₃₎ -, wherein the fluorine-containing copolymer according to item 19.

Section 21.

L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, and also

L ^a is -CH ₂ -O-CH ₂ -CH ₂ -.

Section 22.

L ^{a '} is -CH ₂ -, and

The fluorine-containing copolymer according to any one of items 13 to 20, wherein L ^a is -CH ₂ -.

Section 23.

R ^c is not an organic group containing a curable part,

The fluorine-containing copolymer according to any one of items 1 to 22, wherein at least one Q is a constituent unit containing a curable part.

Section 24.

The fluorine-containing copolymer according to (23), wherein the curable part in Q is a (meth) acryloyl group or a silane coupling group.

Section 25.

The constituent unit containing the curable part is a group bonded to X ^b via a curable addition linker,

Wherein the linker is selected from the group consisting of - (CHR ^y ) _n -O- or - (CHR ^y ) _n -O- (CHR ^y ) _n -O- R ^y represents, at each occurrence, each independently hydrogen or a methyl group)

Wherein the fluorine-containing copolymer is the fluorine-containing copolymer according to item 23 or 24.

Section 26.

The fluorine-containing copolymer according to any one of items 23 to 25, wherein R ^c is a methyl group.

Section 27.

R ^c is a fluorine-containing copolymer according to any one of items 1 to 25, which is an organic group containing a curable part.

Item 28.

The fluorine-containing copolymer according to item 27, wherein R ^c is a group containing a silane coupling group.

Section 29.

The oil repellent and / or water repellent coating agent containing the fluorine-containing copolymer according to any one of items 1 to 28.

Section 30.

Equation (2):

^{_{R r1 -O- (C r F 2r}} O) nd -R r2

[Wherein,

r is, independently for each occurrence, an integer of 1 to 6;

nd represents the number of repetitions.

R ^r1 and R ^r2 each independently represent a perfluoroalkyl group having 1 to 16 carbon atoms, preferably 1 to 3 carbon atoms]

And / or a water repellent coating agent according to item 29,

Section 31.

29. An article containing a coating formed from the oil repellent and / or water repellent coating agent described in item 29 or 30.

Section 32.

expression:

[Wherein,

PFPE represents F- (CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents the number of repeats).

Y ^a represents an acyloxy group or a halogen atom]

&Lt; / RTI >

Poly (perfluoropropyloxy) methoxyethoxyvinyl ether represented by the formula: PFPE-CH ₂ -OC ₂ H ₄ O-CH═CH ₂ (wherein the symbols have the same meanings as defined above)

Y ^a -H (wherein the symbols have the same meanings as defined above)

&Lt; / RTI > with a compound represented by formula (I).

Item 33

expression:

[Wherein,

Y ^a represents an acyloxy group or a halogen atom]

&Lt; / RTI >

Poly (perfluoropropyloxy) methoxy vinyl ether represented by the formula: PFPE-CH ₂ -O-CH = CH ₂ (wherein the symbols have the same meanings as defined above)

Y ^a -H (wherein the symbols have the same meanings as defined above)

Lt; / RTI > with a compound represented by the general formula (I).

Item 34.

expression:

[Wherein,

PFPE _{is, -CF (-CF 3) - (} O-CF 2 -CF (-CF 3)) n -O-CF 2 -Rf-CF 2 -O- (CF (-CF 3) -CF 2 -O -) _{n '} -CF (CF ₃ ) - (Rf represents a perfluoroalkylene group, and n and n' each represent a repetition number).

Y ^a represents an acyloxy group or a halogen atom]

&Lt; / RTI >

_{Formula: CH 2 = CH-OC 2} H 4 -O-CH 2 -PFPE-CH 2 -OC 2 H 4 -O-CH = CH 2 ( Expression of the symbols represents the same meaning as defined above)

&Lt; / RTI >

Y ^a -H (wherein the symbols have the same meanings as defined above)

Lt; / RTI > with a compound represented by the general formula (I).

Item 35.

expression:

[Wherein,

PFPE represents -CF ₂ CF ₂ -O- (CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repetition number).

Y ^a represents an acyloxy group or a halogen atom]

&Lt; / RTI >

Y ^a -H (wherein the symbols have the same meanings as defined above)

Lt; / RTI > with a compound represented by the general formula (I).

Item 36

expression:

[Wherein,

Y ^a represents an acyloxy group or a halogen atom]

&Lt; / RTI >

???????? CH ₂ = CH-O-CH ₂ -PFPE-CH ₂ -O-CH = CH ₂ (wherein the symbols have the same meanings as defined above)

&Lt; / RTI >

Y ^a -H (wherein the symbols have the same meanings as defined above)

&Lt; / RTI > with a compound represented by formula (I).

Item 37.

The production method according to any one of items 32 to 36, wherein the compound represented by the formula: Y ^a -H is CF ₃ COOH.

The fluorine-containing copolymer of the present invention can be suitably used as a oil repellent and / or water repellent coating agent, having excellent oil repellency and / or water repellency and high solubility in a general solvent (fluorine-free organic solvent).

1 is a graph of MALDI-TOF-MS.

1. Terminology

In the specification, unless otherwise stated, the symbol " to " indicating the numerical range is used with the numerical value at both ends thereof being intended to be included in the numerical range.

In the present specification, unless otherwise specified, the "perfluoropolyether group" is a monovalent or divalent "perfluoropolyether group". The "monovalent perfluoropolyether group" means a perfluoroalkyl group having at least one carbon-carbon bond with an etheric oxygen atom inserted therein. The "divalent perfluoropolyether group" means a perfluoroalkylene chain having at least one carbon-carbon bond with an etheric oxygen atom inserted therein. In the present specification, the perfluoropolyether group may be represented by the abbreviation: PFPE.

In the present specification, unless otherwise specified, the "perfluoroalkyl group" includes, for example, perfluoroalkyl groups having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3) . The "perfluoroalkyl group" may be straight-chain or branched, but is preferably straight-chain.

The "perfluoroalkyl group" may be a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, or may be a group in which all the hydrogen atoms other than one hydrogen atom at the terminal of the alkyl group are substituted with fluorine atoms. , Preferably all hydrogen atoms of the alkyl group are substituted with fluorine atoms.

In the present specification, the "perfluoroalkylene chain" means a group in which all the hydrogen atoms other than one hydrogen atom at the terminal of the alkyl group in the "perfluoroalkyl group" are derived from the group in which the hydrogen atom has been substituted with a fluorine atom Means a divalent group. The "perfluoroalkylene chain" is, for example, a perfluoroalkylene chain having 1 to 12 (preferably 1 to 6, more preferably 1 to 3) carbon atoms, unless otherwise specified.

The "perfluoroalkylene chain" may be straight-chain or branched, but is preferably straight-chain.

In the present specification, unless otherwise specified, the "alkyl group" includes, for example, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3, and more preferably 1) , An ethyl group, a propyl group, and an isopropyl group). The "alkyl group" may be straight-chain or branched, but is preferably straight-chain.

Unless otherwise stated in the specification, the "alkanoyl group" is, for example, an alkanoyl group having 2 to 13 carbon atoms (preferably 2 to 7, more preferably 2 to 4, and more preferably 2) .

The "alkanoyl group" is a group represented by the formula: RCO- (R represents an alkyl group).

The "alkanoyl group" may be straight-chain or branched, but is preferably straight-chain.

In the present specification, unless otherwise specified, as the " silane coupling group ", for example,

(a) Si (-R ^s ) _m (-OR ^s ) _3-m -

[Wherein,

R ^s represents an alkyl group. And

m represents an integer of 0 to 2,

An alkoxysilyl group (silyl ether group) represented by the formula

(b) Si (-R ^s ) _m (-OCOR ^s ) _3-m -

[Wherein,

R ^s represents an alkyl group. And

m represents an integer of 0 to 2,

An alkylcarbosilyl group;

(c): Si (-R ^s ) _m (-X) _3-m -

[Wherein,

X represents a halogen atom.

R ^s represents an alkyl group. And

m represents an integer of 0 to 2,

A halogenated silane group represented by the formula And

(d) Si (-R ^s ) _m (-R ^N ) _3-m -

[Wherein,

R ^N represents -NR ^s ₂ or -NHR ^s .

R ^s represents an alkyl group. And

m represents an integer of 0 to 2,

And a silazane group represented by the formula In the present specification, such a silane coupling group may be represented simply by Z-.

In the present specification, the term "organic group" means a group containing carbon.

In the present specification, the term " a group containing a perfluoropolyether group " is excluded from " an organic group which may contain a curable part ".

2. Fluorine-containing copolymer

In the fluorine-containing copolymer of the present invention,

Equation (1):

&Lt; / RTI >

Hereinafter, symbols in the formula (1) will be described.

R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group. k is 1 or 2;

The " group containing a perfluoropolyether group " represented by R ^a1 is preferably a monovalent group in which a monovalent " perfluoropolyether group " is bonded via one linker or a divalent " perfluoro Quot; and " polyether group " each are bonded via one linker.

The lower limit of the number average molecular weight of the "perfluoropolyether group" is preferably about 1000, more preferably about 1500, and still more preferably about 2000 from the viewpoint of obtaining high oil repellency and water repellency.

The upper limit of the number average molecular weight of the "perfluoropolyether group" is preferably about 100,000, more preferably about 50,000, still more preferably about 50,000, and still more preferably about 100,000, from the viewpoint of obtaining high solubility in a general solvent (fluorine- It is about 10,000.

The " perfluoropolyether group "

Formula: - (C _p F _2p O) _na -

[Wherein,

na indicates the number of repetitions]

As shown in Fig.

The moiety represented by the formula: C _p F _2p O may be independently the same as or different from each other in repeating na.

The number of repeats represented by na is 1 to 1000. The number of repeats represented by na may be a number-average value in the fluorine-containing copolymer.

The " monovalent group containing a perfluoropolyether group " represented by R ^a1 is preferably a group represented by the formula (a1) described later.

Formula: X ^ra - (C _p F _2p O) _na -Y ^ra -L ^a - (a1)

[Wherein,

p represents, independently for each occurrence, an integer of 1 to 6;

and na represents the number of repeats from 1 to 1000.

Y ^ra represents a perfluoro alkylene chain having 1 to 6 carbon atoms.

L ^a represents a linker]

Hereinafter, the symbols in the formula (a1) will be described.

X ^ra is preferably fluorine or CF ₃ -O-.

p is, independently at each occurrence, an integer of 2 to 3, in each occurrence.

The moiety represented by the formula: (C _p F _2p O) _na is preferably -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O-, -CF ₂ - O-, -CF ₂ -CF ₂ -O- and -CF (-CF ₃ ) -O-.

n a is preferably 1 to 500, more preferably 5 to 150.

^Yra is preferably a group represented by the formula:

_{- (CF 2) fa -CF (} -Z a) - (CF 2) ga -

[Wherein,

and fa and ga independently represent a repetition number that is an integer of 0 or more. The sum of fa and ga is an integer of 0 to 5.

Z ^a represents fluorine or -CF ₃ ]

, More preferably a group represented by -CF ₂ -, -CF ₂ -CF ₂ - or -CF (-CF ₃ ) -.

In the moiety represented by the formula: - (C _p F _2p O) _na -, preferably,

(1) a moiety represented by the formula (C _p F _2p O) _na includes -CF ₂ -CF ₂ -CF ₂ -O-, and

na is a repeating number of 1 to 1000, preferably 5 to 100;

(2) The moiety represented by the formula (C _p F _2p O) _na includes -CF ₂ -O- and -CF ₂ -CF ₂ -O-,

na is a repeating number of 2 to 1000, preferably 5 to 150;

(3) a moiety represented by the formula (C _p F _2p O) _na contains -CF (-CF ₃ ) -CF ₂ -O-, and

na is a repeating number of 1 to 1000, preferably 5 to 100; or

(4) a moiety represented by the formula (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O- and -CF ₂ -O-,

na is a repeating number of 2 to 1000, preferably 5 to 150.

The moiety represented by the formula: X ^ra - (C _p F _2p O) _na -Y ^ra -

(1) X ^ra is fluorine or R f -O- (R f is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably fluorine,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -CF ₂ -;

(2) X ^ra is fluorine or R f -O- (R f is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably CF ₃ -O-,

The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -O- and -CF ₂ -CF ₂ -O-,

na is a repeating number of 2 to 1000, preferably 5 to 150,

Y ^ra is -CF ₂ -;

(3) X ^ra is fluorine or R f -O- (R f is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y is ^ra, -CF (-CF ₃₎ - or; or

(4) X ^ra is fluorine or R f -O- (R f is a perfluoroalkyl group having 1 to 8 carbon atoms), preferably CF ₃ -O-,

na is a repeating number of 2 to 1000, preferably 5 to 150,

Y ^ra is -CF ₂ -.

L ^a is preferably a single bond or a linker having 1 to 6 (more preferably 1 to 5, 2 to 5, 1 to 4, or 2 to 4) atoms of the main chain.

Examples of such a linker include a single bond, -CH ₂ -, -CH ₂ -O-, -CH ₂ -O-CH ₂ -, -O-CH ₂ -CH ₂ -, -C (= O) -O -, -C (= O) -NH-, -CH ₂ -OC (= O) - and -CH ₂ - (O-CH ₂ -CH ₂ ) _nk 1 - (nk 1 is 1 to 10) .

Among them, preferably -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -. Preferably, the atoms at the left end of the substrate of these partial structures are bonded to perfluoropolyether groups.

As the " monovalent group containing a perfluoropolyether group " represented by R ^a1 , particularly preferably,

(1) In formula (a1)

X ^ra is fluorine,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -CF ₂ -, and

L ^a is ^a group -CH ₂ -O-CH ₂ -CH ₂ -;

(2) In formula (a1)

X ^ra is CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 150,

Y ^ra is -CF ₂ -, and

L ^a is ^a group -CH ₂ -O-CH ₂ -CH ₂ -;

(3) In formula (a1)

X ^ra is CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y is ^ra, -CF (-CF ₃₎ -, and also

L ^a is ^a group -CH ₂ -O-CH ₂ -CH ₂ -;

(4) In formula (a1)

X ^ra is CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 150,

Y ^ra is -CF ₂ -, and

L ^a is ^a group -CH ₂ -O-CH ₂ -CH ₂ -;

(5) In the formula (a1)

X ^ra is fluorine,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -CF ₂ -, and

L ^a is ^a group -CH ₂ -;

(6) In formula (a1)

X ^ra is CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 150,

Y ^ra is -CF ₂ -, and

L ^a is ^a group -CH ₂ -;

(7) In the formula (a1)

X ^ra is CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y is ^ra, -CF (-CF ₃₎ -, and also

L ^a is ^a group -CH ₂ -; or

(8) In formula (a1)

X ^ra is CF ₃ -O-,

na is a repeating number of 1 to 1000, preferably 5 to 150,

Y ^ra is -CF ₂ -, and

L ^a is ^a group -CH ₂ -.

The "perfluoropolyether group-containing divalent group" represented by R ^a1 is preferably a group represented by the following formula (a2) or a group represented by the formula (a2 ').

^???????? - L ^{a '} -Y ^ra' -O- (C _p F _2p O) _na -Y ^ra -L ^a - (a2)

[Wherein,

L ^{a '} and L ^a independently represent a linker.

p represents, independently for each occurrence, an integer of 1 to 6;

na represents the number of repeats from 1 to 1000;

The machine

Hereinafter, symbols in the formula (a2) will be described.

L ^{a '} and L ^a are each independently preferably a single bond or a linker having an atomic number of 1 to 6 (more preferably 1 to 5, 2 to 5, 1 to 4, or 2 to 4) to be. Examples of such a linker represented by L ^{a '} include a single bond, -CH ₂ -, -CH ₂ -CH ₂ -O-, -OC (= O) -, -NH-C C (= O) -O-CH 2 - and _{- (O-CH 2 -CH 2} ) nk1 -CH 2 - (nk1 is from 1 to 10 Im) can be given. Among them, preferably -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -. Preferably, the atoms at the right end of the substrate of these partial structures are bonded to the perfluoropolyether group.

Examples of such linkers represented by L ^a include a single bond, -CH ₂ -, -O-CH ₂ -CH ₂ -, -C (═O) -O-, -C (═O) -NH- , -CH ₂ -OC ( _═O ) - and -CH ₂ - (O-CH ₂ -CH ₂ ) _nk 1 - (nk 1 is 1 to 10). Among them, preferably -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -. Preferably, the atoms at the left end of the substrate of these partial structures are bonded to perfluoropolyether groups.

Y ^{ra '} and Y ^ra are each, independently, preferably

_{Formula: - (CF 2) fa -CF} (-Z a) - (CF 2) ga -

[Wherein,

Z represents fluorine or -CF ₃ ]

More preferably -CF ₂ -, -CF ₂ -CF ₂ - or -CF (-CF ₃ ) -.

p is, independently for each occurrence, an integer of 2 to 4,

The moieties represented by the formula (C _p F _2p O) _na are each independently preferably -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O-, And at least one structural unit selected from the group consisting of -CF ₂ -O-, -CF ₂ -CF ₂ -O- and -CF (-CF ₃ ) -O-.

Each of na is independently preferably from 1 to 500, more preferably from 5 to 150.

In the moiety represented by the formula: - (C _p F _2p O) _na -, preferably,

na is a repeating number of 1 to 1000, preferably 5 to 100;

na is a repeating number of 2 to 1000, preferably 5 to 150;

(3) a moiety represented by the formula (C _pa F _2pa O) _na includes -CF (-CF ₃ ) -CF ₂ -O-, and

na is a repeating number of 1 to 1000, preferably 5 to 100; or

na is a repeating number of 2 to 1000, preferably 5 to 150.

In the moiety represented by the formula: -Y ^{ra '} -O- (C _p F _2p O) _na -Y ^ra -

(1) Y ^{ra 'is,} -CF ₂ -CF ₂ -, and

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -CF ₂ -;

(2) Y ^{ra 'is,} -CF ₂ -, and

na is a repeating number of 2 to 1000, preferably 5 to 100, and

Y ^ra is -CF ₂ -;

(3) Y ^{ra 'is,} -CF (-CF ₃₎ -, and

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y is ^ra, -CF (-CF ₃₎ - or; or

(4) Y ^{ra 'is,} -CF ₂ -, and

na is a repeating number of 2 to 1000, preferably 5 to 100, and

Y ^ra is -CF ₂ -.

^{Formula: -L a '-Y ra' -} (OC p 'F 2p') na '-O-Rf-O- (C p F 2p O) n -Y ra -L a - (a2')

[Wherein,

L ^{a '} and L ^a independently represent a linker.

p 'and p each independently represent an integer of 1 to 6 in each occurrence.

and na and na 'represent the number of repeats from 1 to 1000.

Rf represents a perfluoroalkylene chain]

Hereinafter, symbols in the formula (a2 ') will be described.

L ^{a '} and L ^a are each independently preferably a single bond or a linker having an atomic number of 1 to 6 (more preferably 1 to 5, 2 to 5, 1 to 4, or 2 to 4) to be.

Examples of such a linker represented by L ^{a '} include a single bond, -CH ₂ -, -CH ₂ -CH ₂ -O-, -OC (= O) -, -NH-C -C (= O) -O-CH 2 - and _{- (O-CH 2 -CH 2} ) nk1 -CH 2 - (nk1 is from 1 to 10 Im) can be given. Among them, preferably -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -. Preferably, the atoms at the right end of the substrate of these partial structures are bonded to the perfluoropolyether group.

Examples of such linkers represented by L ^a include a single bond, -CH ₂ -, -O-CH ₂ -CH ₂ -, -C (═O) -O-, -C (═O) -NH- , -CH ₂ -OC ( _═O ) - and -CH ₂ - (O-CH ₂ -CH ₂ ) _nk 1 - (nk 1 is 1 to 10). Among them, preferably -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -. Preferably, the atoms at the left end of the substrate of these partial structures are bonded to perfluoropolyether groups.

Y ^{ra '} and Y ^ra are each, independently, preferably

_{Formula: - (CF 2) fa -CF} (-Z a) - (CF 2) ga -

[Wherein,

Z ^a represents fluorine or -CF ₃ ]

More preferably -CF ₂ -, -CF ₂ -CF ₂ - or -CF (-CF ₃ ) -.

The moiety represented by the formula OC _{p '} F _2p' may be independently the same as or different from each other in repeating na '.

p 'is, for each occurrence, independently of each other, preferably an integer of 2 to 4.

The moieties represented by the formula: (OC _{p '} F _2p' ) _{na '} are each independently preferably -O-CF ₂ -CF ₂ -CF ₂ -, -O-CF ₂ -CF (-CF ₃ ) -, -O-CF ₂ -, -O-CF ₂ -CF ₂ - and -O-CF (-CF ₃ ) -.

independently of one another, preferably from 1 to 500, more preferably from 5 to 150,

p is, independently for each occurrence, an integer of 2 to 4,

Rf is preferably a perfluoro alkylene chain having 1 to 8 carbon atoms.

In the moiety represented by the formula: -Y ^{ra '} - (OC _p' F _{2p '} ) _na' -O-Rf-O- (C _p F _2p O) _na -Y ^ra -

Y ^{ra 'is,} -CF (-CF ₃₎ - is;

Rf is a perfluoroalkylene chain having 1 to 8 carbon atoms;

Y is ^ra, -CF (-CF ₃₎ - a.

As the "perfluoropolyether group-containing divalent group" represented by R ^a1 , particularly preferably,

(1) In formula (a2)

L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -

Y ^{ra '} is -CF ₂ -CF ₂ -

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -CF ₂ -, and

L ^a is -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -;

(2) In formula (a2)

L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -

Y ^{ra '} is -CF ₂ -

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -, and

L ^a is -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -;

(3) In formula (a2)

L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -

Y ^{ra '} is -CF (-CF ₃ ) -,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y is ^ra, -CF (-CF ₃₎ -, and also

L ^a is -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -; or

(4) In formula (a2)

L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ - or -CH ₂ -

Y ^{ra '} is -CF ₂ -

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^ra is -CF ₂ -, and

L ^a is -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -; or

(5) In formula (a2 '),

L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -

Y ^{ra '} is -CF (-CF ₃ ) -,

The moiety represented by the formula: (OC _{p '} F _2p' ) _{na '} includes -O-CF ₂ -CF (-CF ₃ ) -,

na 'is a repeating number of 1 to 1000, preferably 5 to 100,

Rf is a perfluoroalkylene chain having 1 to 8 carbon atoms,

na is a repeating number of 1 to 1000, preferably 5 to 100,

Y is ^ra, -CF (-CF ₃₎ -, and also

L ^a is a group -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -.

In the present specification, phenylene (which may be abbreviated as -Ph-) may be represented by the following formula:

And is preferably represented by

to be.

As an organic group represented by R ^E , for example, an alkyl group can be mentioned.

In the present specification, carbazolylene has the following formula:

And is preferably represented by

to be. Here, the nitrogen atom in the formula is bonded to the carbon atom in the formula (1).

X ^a is preferably -O-, -Ph- or carbazolylene, more preferably -O- or -Ph-, and more preferably -O-.

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a2 is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

R ^a3 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Provided that at least one of R ^a2 and R ^a3 is an alkyl group.

Q each independently represent a constituent unit containing a curable part (hereinafter sometimes referred to as a constituent unit Q ^b ) or a constituent unit not containing a curable constituent (hereinafter referred to as constituent unit Q ^m ).

n1 is the number of repeating structural units represented by Q, and is an integer of 1 or more.

n1 is preferably 1 to 200, more preferably 5 to 100, and still more preferably 5 to 35.

The formula in the formula (1)

Part is represented by, and may be composed only of the structural unit Q ^b, the structural unit may be constituted only by Q ^m, or the configuration is the unit may be composed of a Q ^b and Q structural unit ^m.

However, when R ^c described later is not an organic group containing a curable part, the above-mentioned moiety must contain at least one constituent unit Q ^b . In other words, in this case, at least one Q is configured to contain parts of curing unit Q ^b.

The structural unit Q ^b and structural units Q ^m, respectively, and may form a block, or may, and randomly combined.

Q is preferably a group represented by the formula:

.

R ^b1 is preferably a hydrogen atom.

That is, R ^b2 is independently an organic group containing a hydrogen atom, a curable part, or an organic group which does not contain a curable part, at each occurrence of n1 times.

Hereinafter, R ^b2 is an organic group containing a curable part,

May be abbreviated as the constituent unit B in some cases.

Hereinafter, R ^b2 is an organic group containing no hydrogen atom or a curable part,

May be abbreviated as the constitutional unit M.

The " organic group containing a curable component " represented by R ^b2 is preferably a group bonded to X ^b through a curable additional linker.

Examples of the curable part in the "organic group containing a curable part" represented by R ^b2 include allyl group, cinnamic acid group, sorbic acid group, (meth) acryloyl group and silane coupling group. Among them, a (meth) acryloyl group or a silane coupling group is preferable, and silyl group and methacryloyl group are particularly preferable.

The preferred hardenable part depends on the material of the coating.

When the material is an amorphous synthetic resin (e.g., an acrylic resin), the "curable part" is preferably an allyl group, a cinnamic acid group, a sorbic acid group, or CH ₂ ═CR ^x -C (═O) - (R ^x is hydrogen, a methyl group, chlorine or fluorine) (e.g., a (meth) acryloyl group), and more preferably a (meth) acryloyl group.

When the material is free, the "curable part" is preferably a silane coupling group, more preferably a silazane group.

The " linker " is preferably a linker having 1 to 16 (more preferably 2 to 12, still more preferably 4 to 10) atoms in the main chain.

For example, when the "curable part" is an allyl group, a cinnamic acid group, a sorbic acid group or a (meth) acryloyl group, the "linker"

(a) - (CH ₂ -CH ₂ -O) _n - (n is an integer of 2 to 10),

(b) - (CHR ^y ) _n -O-, or - (CHR ^y ) _n -O- (CHR ^y ) _n -O- wherein n is an integer of 1 to 40, R ^y represents, independently of each other, hydrogen or a methyl group),

(c) - (CH ₂ -CH ₂ -O) _n -CO-NH-CH ₂ -CH ₂ -O- wherein n represents an integer of 2 to 10,

_{(d) -CH 2 -CH 2 -O} -CH 2 -CH 2 -

(e) - (CH ₂ ) _n - (n represents an integer of 1 to 6), or

_{(f) - (CH 2)} nk1 -O-CONH- (CH 2) nk2 -. (nk1 is an integer from 1 to 8, preferably 2 or 4 indicates the nk2 is an integer from 1 to 6, preferably 3 , Or

(g) -O- (wherein X ^b is not -O-)

More preferably -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O- or -CH ₂ -CH ₂ -O-.

Further, for example, when the "curable part" is a silane coupling group, the "linker"

- (CH ₂ ) _n - (n is an integer of 1 to 6), or

_{- (CH 2) nk1 -O-} CONH- (CH 2) nk2 - is the (. Nk1 represents an integer of 1 to 8 nk2 is an integer of 1 to 6), more preferably - (CH _{2) 2} - or - (CH ₂ ) ₃ -.

The " organic group containing no curing moiety " represented by R ^b2 is a group in which a group R ^m described below is bonded to the X ^b or via a linker.

The linker preferably comprises

(a) - (CH ₂ -CH ₂ -O) _n - (n is an integer of 2 to 10),

(b) - (CHR ^y ) _n -O- or - (CHR ^y ) _n -O- (CHR ^y ) _n -O- (n in each occurrence is independently an integer of 1 to 40, , R ^y represents, independently at each occurrence, hydrogen or a methyl group),

_{(d) -CH 2 -CH 2 -O} -CH 2 -CH 2 -,

(e) - (CH ₂ ) _n - (n represents an integer of 1 to 6), or

(g) -O- (wherein X ^b is not -O-)

to be.

R ^m is preferably the following group.

(i) an alkyl group

Examples include methyl, ethyl

(ii) a chain containing an alkyl group substituted with fluorine

Yes:

(iii) a group containing at least one cyclic moiety selected from the group consisting of a monocyclic carbon ring, a bicyclic carbon ring, a tricyclic carbon ring and a tetracyclic carbon ring

Yes:

(iv) a group containing one or more (preferably one or two) hydrocarbon groups substituted with a carboxyl group

Yes:

(v) a group containing one or more (preferably one) amino groups

(vi) hydrogen

(vii) a group containing an imidazolium salt

Yes:

R ^m is more preferably a hydrogen atom or an alkyl group which may be fluorinated and may also be bonded via an ethylene chain, more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group or R ^x -CF ₂ _{- (CF 2) nk1 - (} CH 2) nk2 -O- (CH 2) 2 - (R x is a fluorine atom or a hydrogen atom, nk1 is an integer from 0 to 6 and nk2 is an integer from 1 to 6) and, more preferably, 3- (perfluoroethyl) propoxy group [rational _{formula: CF 3 - (CF 2)} - (CH 2) 3 -O- (CH 2) 2 -] a.

R ^b3 represents, independently at each occurrence, a hydrogen atom or an alkyl group.

R ^b3 is preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom.

X ^b represents -O-, -Ph-, -N (-R ^E ) -, or carbazolylene. Wherein R ^E represents an organic group.

Provided that when R ^b2 is a hydrogen atom, X ^b is -Ph-.

X ^b is preferably -O-, -Ph-, or carbazolylene, more preferably -O- or -Ph-, and more preferably -O-.

Examples of Q ^b include the following structural units.

(a) Formula:

[Wherein,

n represents a repeating number which is an integer of 1 to 6;

R ^x represents hydrogen or a methyl group]

(Meth) acryloyl group-containing structural unit

Yes:

(b)

[Wherein,

n represents a repeating number which is an integer of 1 to 6;

R ^x represents hydrogen or a methyl group]

(Meth) acryloyl group-containing structural unit

Yes:

(c) a structural unit having a silane coupling group

Yes:

(Wherein Z represents a silane coupling group)

Examples of Q ^m include the following structural units.

(a) a structural unit having a cyclic moiety

Yes:

Preferable examples of Q ^b include the following constitutional units.

(a1)

Wherein n represents an integer of 1 to 6;

R ^b2 represents a (meth) acryloyl group]

(a2)

Wherein n represents an integer of 1 to 6 in each occurrence independently of each other.

R ^b2 represents a (meth) acryloyl group]

(E.g., -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-COC (CH ₃ ) = CH ₂ )

(b)

Wherein n represents an integer of 1 to 6;

R ^b2 represents a silane coupling group]

Preferable examples of Q ^m include the following constitutional units.

Wherein n represents an integer of 1 to 6;

R ^b2 represents an alkyl group]

In one aspect of the present invention, R ^c is a monovalent group containing a monovalent perfluoropolyether group.

In this form, the fluorine-containing copolymer of the present invention contains a perfluoropolyether group at both ends, and particularly excellent water repellency is obtained.

As the "monovalent group containing a monovalent perfluoropolyether group" represented by R ^c , a group in which the "monovalent perfluoropolyether group" is bonded via one linker can be exemplified.

The lower limit of the number average molecular weight of the "monovalent perfluoropolyether group" is preferably about 1,000, more preferably about 1,500, and still more preferably about 2,000, from the viewpoint of obtaining high oil repellency and / or water repellency to be.

The upper limit of the number average molecular weight of the "monovalent perfluoropolyether group" is preferably about 100,000, more preferably about 50,000, more preferably about 100,000, from the viewpoint of obtaining high solubility in a general solvent (fluorine-free organic solvent) More preferably about 10,000.

The "monovalent group containing a monovalent perfluoropolyether group" is preferably a group represented by the following formula (c1).

^{_{Formula: R c '- (C q}} F 2q O) nc -Y c -L c - (c1)

[Wherein,

R ^{c '} represents fluorine or R f ^c -O- (R f ^c represents a perfluoroalkyl group having 1 to 8 carbon atoms).

q independently represents an integer of 1 to 6 in each occurrence.

nc represents the number of repeats of 1 to 1000.

Y ^c represents a perfluoroalkylene chain having 1 to 6 carbon atoms.

L ^c represents a linker]

Lt; / RTI >

Hereinafter, symbols in the above formula (c1) will be described.

R ^{c '} is preferably fluorine or CF ₃ -O-.

The moiety represented by the formula: C _q F _2q O may be independently the same or different in n c repetitions.

q is, for each occurrence, independently of each other, preferably an integer of 2 to 3.

The moiety represented by the formula: (C _q F _2q O) _nc is preferably -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O-, -CF ₂ - O-, -CF ₂ -CF ₂ -O- and -CF (-CF ₃ ) -O-.

nc is preferably from 1 to 500, more preferably from 5 to 150.

Y ^c is preferably

- (CF ₂ ) _f ^c -CF (-Z ^c ) - (CF ₂ ) _g ^c -

[Wherein,

fc and gc independently represent a repetition number that is an integer of 0 or more. The sum of fc and gc is an integer of 0 to 5.

Z ^c represents fluorine or -CF ₃ ]

Formula: - is preferably at the portion represented _{by, - (C q F 2q O} ) nc

(1) a moiety represented by the formula (C _q F _2q O) _nc includes -CF ₂ -CF ₂ -CF ₂ -O-, and

nc is a repeating number of 1 to 1000, preferably 5 to 100;

(2) formula: (C _q F _2q O) portion is represented by _nc, including -CF ₂ -O-, and -CF ₂ -CF ₂ -O-, and further

nc is a repeating number of 2 to 1000, preferably 5 to 150;

(3) formula: (C _q F _2q O) portion is represented by _nc, including -CF (-CF ₃₎ -CF ₂ -O-, and further

nc is a repeating number of 1 to 1000, preferably 5 to 100; or

4 formula: (C _q F _2q O) portion is represented by _nc, including -CF (-CF ₃₎ -CF ₂ -O-, and -CF ₂ -O-, and further

nc is a repeating number of 2 to 1000, preferably 5 to 150.

Formula: R ^{c '-} it is preferably at the portion represented _{by, - (C q F 2q O} ) nc -Y c

(1) R ^{c '} is fluorine,

The moiety represented by the formula: (C _q F _2q O) _nc includes -CF ₂ -CF ₂ -CF ₂ -O-,

nc is a repeating number of 1 to 1000, preferably 5 to 100, and

Y ^c is -CF ₂ -CF ₂ -;

(2) R ^{c '} is CF ₃ -O-,

The moiety represented by the formula: (C _q F _2q O) _nc includes -CF ₂ -O- and -CF ₂ -CF ₂ -O-,

nc is a repeating number of 2 to 1000, preferably 5 to 150,

Y ^c is -CF ₂ -;

(3) R ^{c '} is CF ₃ -O-,

The moiety represented by the formula: (C _q F _2q O) _nc includes -CF (-CF ₃ ) -CF ₂ -O-,

nc is a repeating number of 1 to 1000, preferably 5 to 100, and

Y ^c is -CF (-CF ₃ ) -; or

(4) R ^{c '} is CF ₃ -O-,

The moiety represented by the formula: (C _q F _2q O) _nc includes -CF (-CF ₃ ) -CF ₂ -O- and -CF ₂ -O-,

nc is a repeating number of 2 to 1000, preferably 5 to 150,

Y ^c is -CF ₂ -.

L ^c is preferably a linker having 1 to 6 (preferably 1 to 5, more preferably 1) atoms in the main chain.

The linker is preferably -CH ₂ -O-CH ₂ -CH ₂ - or -CH ₂ -, more preferably -CH ₂ -.

The "perfluoropolyether group-containing monovalent group" represented by R ^c is particularly preferably a group represented by the formula (c1)

(1) R ^{c '} is fluorine,

nc is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^c is -CF ₂ -CF ₂ -, and

L ^c is a group -CH ₂ -O-CH ₂ -CH ₂ -;

(2) R ^{c '} is CF ₃ -O-,

nc is a repeating number of 1 to 1000, preferably 5 to 150,

Y ^c is -CF ₂ -, and

L ^c is a group -CH ₂ -O-CH ₂ -CH ₂ -;

(3) R ^{c '} is CF ₃ -O-,

nc is a repeating number of 1 to 1000, preferably 5 to 100,

Y ^c is -CF (-CF ₃ ) -, and

L ^c is a -CH ₂ -O-CH ₂ -CH ₂ group; or

(4) R ^{c '} is CF ₃ -O-,

nc is a repeating number of 1 to 1000, preferably 5 to 150,

Y ^c is -CF ₂ -, and

L ^c is a group -CH ₂ -O-CH ₂ -CH ₂ -

to be.

In another aspect of the present invention, R ^c is preferably an organic group which may contain a curable part.

When R ^c is an organic group not containing a curable part, examples of the "organic group not containing a curable part" include an alkanoyl group and an alkyl group. Among them, an alkyl group is preferable, and a methyl group is particularly preferable.

When R ^c is an organic group containing a curable part, the "organic group containing a curable part" is preferably a group bonded to X ^c through a curable addition linker.

Examples of the "curable part" include an allyl group, a cinnamic acid group, a sorbic acid group, a (meth) acryloyl group and a silane coupling group. Among them, a silane coupling group is preferable.

The "linker" is preferably a linker having 1 to 6 atoms in the main chain.

Among them, when the "curable component" is a (meth) acryloyl group, the "linker" is preferably - (CH ₂ ) _n - (n is 1 to 6) -CH ₂ CH ₂ -.

On the other hand, the art when "curing unit" is a silane coupling Ferringhi, the art "linker" is preferably _{- (CH 2) n - (} n is 1-6 being), and more preferably - (CH ₂₎ ₃ -to be.

When the material to be coated is an amorphous synthetic resin (e.g., an acrylic resin), the "curable part" is preferably an allyl group, a cinnamic acid group, a sorbic acid group or a (meth) acryloyl group, (Meth) acryloyl group.

On the other hand, when the material to be coated is glass, the "curable part" is preferably a silane coupling group.

X ^c represents -O-, -S-, -NH- or a single bond. Preferably -O-, -NH-.

One preferred form of the fluorine-containing copolymer of the present invention is a fluorine-

R ^b2 is an organic group which may contain a hydrogen atom or a curing moiety in each occurrence independently,

R ^c represents an organic group not containing a curable part.

Provided that at least one of the groups represented by R ^b2 is an organic group containing a curable part and the curable part is a fluorine-containing copolymer which is a (meth) acryloyl group.

Another preferred embodiment of the fluorine-containing copolymer of the present invention is a fluorine-

R ^b2 is an organic group which, at each occurrence, independently contains a hydrogen atom or a curable part,

R ^c is a fluorine-containing copolymer which is an organic group containing a silane coupling group as a curable part.

3. Method for producing fluorine-containing copolymer

The fluorine-containing copolymer of the present invention is obtained by the following steps:

(1) a step of cationically polymerizing a cationic polymerizable monomer in the presence of a perfluoropolyether group-containing cationic polymerization initiator and a Lewis acid, and

(2) a step of stopping the cationic polymerization reaction by using a cationic polymerization terminator (step 2).

3.1. Process 1

3.1.1. A perfluoropolyether group-containing cationic polymerization initiator

The " perfluoropolyether group-containing cationic polymerization initiator " (open type) used in Step 1 is a cationic polymerization initiator containing a monovalent or divalent perfluoropolyether group.

As the "cationic polymerization initiator containing a monovalent perfluoropolyether group", for example,

(a) Formula:

R ^a1 -X ^a -C (-R ^a2 ) (-R ^a3 ) -O-CO-R ^a4

[Wherein,

R ^a1 represents a monovalent group containing a monovalent perfluoropolyether group.

X ^a represents -O-, -Ph-, -N (-R ^E ) - (wherein R ^E represents an organic group).

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group.

R ^a4 represents an alkyl group or a perfluoroalkyl group.

Provided that at least one of R ^a2 and R ^a3 is an alkyl group.

Or a compound represented by formula

(b)

R ^a1 -X ^a -C (-R ^a2 ) (-R ^a3 ) -X ^c

[Wherein,

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group

Provided that at least one of R ^a2 and R ^a3 is an alkyl group,

X ^c represents a halogen atom]

And the like.

As the " cation polymerization initiator containing a bivalent perfluoropolyether group ", for example,

(c) Formula:

^{R a4 -CO-OC (-R a2} ) (- R a3) -X a -R a1 -X a -C (-R a2) (- R a3) -O-CO-R a4

[Wherein,

R ^a1 represents a divalent group containing a divalent perfluoropolyether group.

R ^a2 represents a hydrogen atom or an alkyl group. And

R ^a3 represents a hydrogen atom or an alkyl group.

Provided that at least one of R ^a2 and R ^a3 is an alkyl group,

R ^a4 represents an alkyl group or a monovalent perfluoroalkyl group]

Or a compound represented by the formula

(d)

X ^c --C (- R ^a2 ) (-R ^a3 ) -X ^a -R ^a1 -X ^a -C (-R ^a2 ) (-R ^a3 ) -X ^c

[Wherein,

R ^a2 represents a hydrogen atom or an alkyl group.

R ^a3 represents a hydrogen atom or an alkyl group. And

X ^c represents a halogen atom.

Provided that at least one of R ^a2 and R ^a3 is an alkyl group.

And the like.

Specific examples of the "cationic polymerization initiator containing a monovalent perfluoropolyether group" include the following compounds, for example.

[In the formula, PFPE is a monovalent perfluoropolyether chain

(Preferably, F- (CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repeating number)). X represents a halogen atom. Other symbols have the same meanings as above]

Specific examples of the " cationic polymerization initiator containing a bivalent perfluoropolyether group " include, for example, the following compounds.

[Wherein,

PFPE is a divalent perfluoropolyether group

(Preferably,

_{(i) -CF (-CF 3)} - (O-CF 2 -CF (-CF 3)) n '-O-CF 2 -Rf-CF 2 -O- (CF (-CF 3) -CF 2 O -) _n -CF (-CF ₃ ) - (Rf represents a perfluoroalkylene chain, n and n 'each represent the number of repeating units), or

_{(ii) -CF 2 CF 2 O-} (CF 2 CF 2 CF 2 O) n -CF 2 CF 2 - (n represents the number of repetitions))

.

Other symbols have the same meanings as above]

The " perfluoropolyether group-containing cationic polymerization initiator "

(Wherein the symbols have the same meanings as defined above)

, And more preferably

(Wherein the symbols have the same meanings as defined above)

to be.

When the above "perfluoropolyether group-containing cationic polymerization initiator" is a cationic polymerization initiator containing a monovalent perfluoropolyether group, the compound is represented by the formula: F- (CF ₂ -CF ₂ -CF ₂ -O) _{n -CF 2 -CF 2 -CH 2 OC} 2 H 4 O-CH = CH 2 (n represents the number of repetition) are [3-poly represented by (perfluoro propyl oxy) -2,2,3,3 -Tetrafluoropropoxy] ethoxy vinyl ether with an organic carboxylic acid (preferably acetic acid, trifluoroacetic acid, more preferably trifluoroacetic acid) or hydrogen halide.

For example, the expression:

[Wherein,

PFPE represents F- (CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (n is a repetition number).

Y ^a represents an acyloxy group (e.g., CF ₃ COO) or a halogen atom]

&Lt; / RTI >

Poly (perfluoropropyloxy) methoxyethoxyvinylether (vinyl) represented by the formula: PFPE-CH ₂ -OC ₂ H ₄ O-CH═CH ₂ (wherein the symbols have the same meanings as defined above) The ether compound a)

Y ^a -H (wherein the symbols have the same meanings as defined above)

(Preferably CF ₃ COOH) represented by the formula

&Lt; / RTI >

Similarly,

expression:

[Wherein,

Y ^a represents an acyloxy group or a halogen atom]

Lt; RTI ID = 0.0 >

Y ^a -H (wherein the symbols have the same meanings as defined above)

(Preferably CF ₃ COOH) represented by the formula

&Lt; / RTI >

On the other hand, when the above "perfluoropolyether group-containing cationic polymerization initiator" is a cationic polymerization initiator containing a divalent perfluoropolyether group, the compound has the formula: CH ₂ ═CH-O-CH ₂ -CH ₂ _{-O-CH 2 -CF (-CF 3} ) - (O-CF 2 -CF (-CF 3)) n -O-CF 2 -Rf-CF 2 -O- (CF (-CF 3) -CF 2 -O-) _{n '} -CF (-CF ₃ ) -CH ₂ OC ₂ H ₄ O-CH = CH ₂ (wherein Rf represents a perfluoroalkylene chain, n and n' (Preferably acetic acid, trifluoroacetic acid (CF ₃ COOH), more preferably trifluoroacetic acid) or hydrogen halide in the presence of a base.

For example, the expression:

[Wherein,

Y ^a represents an acyloxy group (e.g., CF ₃ COO), or a halogen atom]

&Lt; / RTI >

(Vinyl ether compound b) represented by the formula

Y ^a -H (wherein the symbols have the same meanings as defined above)

(Preferably CF ₃ COOH) represented by the formula

&Lt; / RTI >

Also, for example,

[Wherein,

Y ^a represents an acyloxy group or a halogen atom]

&Lt; / RTI >

Y ^a -H (wherein the symbols have the same meanings as defined above)

(Preferably, CF ₃ COOH) represented by the following general formula ( ₁ ).

Similarly,

[Wherein,

Y ^a represents an acyloxy group or a halogen atom]

Lt; RTI ID = 0.0 >

A compound represented by the formula: CH ₂ ═CH-O-CH ₂ -PFPE-CH ₂ -O-CH═CH ₂ (wherein the symbols have the same meanings as defined above)

Y ^a -H (wherein the symbols have the same meanings as defined above)

(Preferably, CF ₃ COOH) represented by the following general formula ( ₁ ).

This production process is a novel process for producing a compound represented by formula (Ia), formula (Ia), formula (Ib), formula (Ib ') or formula (Ib ").

The reaction is preferably carried out in the presence of an acid in a solvent which does not adversely affect the reaction.

As such an acid, an inorganic acid such as hydrochloric acid is preferable. The amount of the acid to be used is usually 0.01 to 1000 mol based on 1 mol of the vinyl ether compound a or the vinyl ether compound b.

As such a solvent, a fluorine-containing solvent such as HCFC-225 is preferable.

The reaction temperature is usually -78 to 50 占 폚, preferably -10 to 10 占 폚.

The reaction time is usually from 1 minute to 60 minutes.

Such a cationic polymerization initiator may be represented by the following formula (1) in the fluorine-containing copolymer of the present invention:

[Wherein the symbols have the same meanings as defined above]

As shown in FIG.

When R ^a1 is a divalent group, the moiety is actually a

expression:

. &Lt; / RTI >

The concentration of the perfluoropolyether group-containing cationic polymerization initiator in the reaction system of Step 1 is preferably 0.1 to 1000 mM, more preferably 1 to 100 mM.

3.1.2. The cationic polymerizable monomer

The cationic polymerizable monomer used in Step 1 is a monomer corresponding to the constituent unit Q.

For example, among the fluorine-containing copolymers produced by this production method,

In the case of synthesizing a fluorine-containing copolymer composed of only the constituent unit B, a part represented by the formula (1) (hereinafter, the part is sometimes referred to as part (b)

^Wherein R ^b2 is an organic group containing a curable part and the symbols in other formulas have the same meanings as defined above,

(Hereinafter sometimes referred to as cationic polymerizable monomer B) is used.

Preferable examples of the monomer corresponding to the constituent unit Q ^b include the following compounds having a (meth) acryloyl group as the curable group.

(a) Formula:

[Wherein,

n represents a repeating number which is an integer of 2 to 10;

R ^x represents hydrogen, methyl group, chlorine or fluorine]

Lt; / RTI >

Specific examples of the vinyl ether compound:

(b)

CH ₂ = CH-O- (CHR ^y ) _n -OC (= O) -CR ^x = CH ₂

[Wherein,

n represents a repetition number which is an integer of 1 to 40;

R ^y represents hydrogen or a methyl group.

R ^x represents hydrogen, methyl group, chlorine or fluorine]

&Lt; / RTI >

Specific examples of the vinyl ether compound:

(c) Formula:

[Wherein,

n represents a repeating number which is an integer of 1 to 10;

R ^x represents hydrogen, methyl group, chlorine or fluorine]

Lt; / RTI >

Specific examples of the vinyl ether compound:

(d)

_{CH 2 = CH-O- (CH} 2) n -OC (= O) -NH-CH 2 CH 2 -OC (= O) -CX = CH 2

[Wherein,

n represents a repetition number which is an integer of 1 to 40;

X represents hydrogen, methyl group, chlorine or fluorine]

Lt; / RTI >

Specific examples of the vinyl ether compound:

(e)

[Wherein,

n represents a repeating number which is an integer of 1 to 10;

R ^x represents hydrogen, methyl group, chlorine or fluorine.

R ^y represents hydrogen or a methyl group]

&Lt; / RTI >

Specific examples of the styrene compound:

(f) Formula:

[Wherein,

n represents a repeating number which is an integer of 1 to 6;

R ^x represents hydrogen or a methyl group]

&Lt; / RTI >

Specific examples of the epoxy compound:

(g) Formula:

[Wherein,

n represents a repeating number which is an integer of 1 to 6;

R ^x represents hydrogen or a methyl group]

(2) < / RTI >

Specific examples of the epoxy compound:

Another preferred example of the monomer B corresponding to the constituent unit Q ^b is the following compound having a silane coupling group as a curable group.

(a) Formula:

CH ₂ = CH-O- (CH ₂ ) _n -Z

[Wherein,

n represents a repetition number which is an integer of 1 to 40;

Z represents a silane coupling group]

&Lt; / RTI >

(b) Specific examples of the vinyl ether compound:

expression:

CH ₂ = CH-O- (CH ₂ ) ₃ -Z

[Wherein the symbols have the same meanings as defined above]

&Lt; / RTI >

(c) Formula:

CH ₂ = CH-ORO- (CH ₂ ) _n -Z

[Wherein,

R represents ethylene or phenylene.

n represents an integer of 1 to 6;

Z represents a silane coupling group]

&Lt; / RTI >

(d) Specific examples of the vinyl ether compound:

(Z represents a silane coupling group)

(e)

[Wherein,

n represents a repeating number which is an integer of 1 to 10;

Z represents a silane coupling group]

Lt; / RTI >

Preferred specific examples of the urethane compound are:

(Z represents a silane coupling group)

(f) Formula:

[Wherein,

n represents a repetition number which is an integer of 1 to 12;

Z represents a silane coupling group]

(2). &Lt; / RTI >

Preferred specific examples of the styrene compound:

(Z represents a silane coupling group)

(g) an epoxy compound having one epoxy group and one silane coupling group.

Preferred specific examples of the epoxy compound include:

(In the formula, Z represents a silane coupling group)

(h) Formula:

[Wherein,

n represents a repeating number which is an integer of 0 to 10;

Z represents a silane coupling group]

&Lt; / RTI >

Preferred specific examples of the styrene compound include:

(In the formula, Z represents a silane coupling group)

For example, in the case of synthesizing a fluorine-containing copolymer in which the moiety (b) is composed only of the constituent unit (M), it is preferable to use, as the cationic polymerizable monomer,

Wherein R ^b2 is an organic group containing no hydrogen atom or a curable part and the other symbols have the same meanings as defined above,

(Hereinafter sometimes referred to as a cationic polymerizable monomer M) is used.

Preferable examples of the monomer corresponding to the constituent unit Q ^m include the following compounds which do not have a curable group.

(a) Formula:

CH ₂ = CH-OR

[Wherein,

R represents a monovalent organic group. Provided that the monovalent organic group does not contain both -OH group, -COOH group and -NH ₂ group.]

&Lt; / RTI >

Examples of the compound include the following compounds.

(i) Formula:

[Wherein,

n represents an integer of 1 to 10;

R ¹ represents an alkyl group]

&Lt; / RTI >

Specific examples of the vinyl ether compound:

(ii) Formula:

[Wherein,

n represents an integer of 1 to 10;

R ¹ represents an alkyl group substituted by at least one fluorine atom]

Lt; / RTI >

Specific examples of the vinyl ether compound:

(iii) a vinyl ether compound containing at least one cyclic moiety selected from the group consisting of a monocyclic carbon ring, a bicyclic carbon ring, a tricyclic carbon ring and a tetracyclic carbon ring.

Specific examples of the vinyl ether compound:

(iv)

[Wherein,

n represents an integer of 1 to 10;

R ¹ represents a hydrocarbon group substituted with at least one (preferably 1 or 2) alkoxycarbonyl groups,

&Lt; / RTI >

As the "hydrocarbon group", for example,

Specific examples of the vinyl ether compound:

When the vinyl ether compound is used, the carboxyl group can be introduced into the fluorine-containing copolymer of the present invention by hydrolyzing the alkoxycarbonyl group, if desired, after the polymerization reaction.

(V) vinyl ether compounds containing at least one (preferably one) amino group protected by imidization or amidation.

Specific examples of the vinyl ether compound:

When the vinyl ether compound is used, the amino group can be introduced into the fluorine-containing copolymer of the present invention by deprotecting the protected amino group, if desired, after the polymerization reaction.

(vi) a vinyl ether compound containing at least one protected (preferably one) hydroxyl group.

Specific examples of the vinyl ether compound:

When the vinyl ether compound is used, the hydroxyl group can be introduced into the fluorine-containing copolymer of the present invention by deprotecting the protected hydroxyl group, if desired, after the polymerization reaction.

(vii) a vinyl ether compound containing an imidazolium salt.

Specific examples of the vinyl ether compound:

(viii) Formula:

[Wherein,

X represents hydrogen or a methyl group.

Ring A represents benzene, or naphthalene.

R represents hydrogen, halogen, or a monovalent organic group. Provided that the monovalent organic group does not contain both -OH group, -COOH group and -NH ₂ group.]

&Lt; / RTI >

Specific examples of the aryl vinyl derivative include:

(ix) Other compounds

For example, in the case of synthesizing a fluorine-containing copolymer in which the moiety (b) is composed of the constituent units B and M, the cationic polymerizable monomer B and the cationic polymerizable monomer M are used as the cationic polymerizable monomer.

Here, in the case of synthesizing the fluorine-containing copolymer in which the constituent units B and M form a block in the part (b), the cationic polymerizable monomers B and M are subjected to cationic polymerization in this order.

Specifically, only the first cationic polymerizable monomer (cationic polymerizable monomer B or M) is added to the reaction system to initiate the polymerization reaction, and the second cationic polymerizable monomer (cationic polymerizable monomer Monomer M or B) is added, in the course of the living cationic polymerization, the cation is always present at the end of the polymer, and therefore the polymerization reaction of the second cationic polymerizable monomer proceeds.

On the other hand, in the case of synthesizing a fluorine-containing copolymer in which the constituent units B and M are randomly bonded in the portion (b) of the fluorine-containing copolymer of the present invention, it is preferable that both of the cationic polymerizable monomers B and M Is added to the reaction system to initiate the polymerization reaction.

These cationic polymerizable monomers B and M can be obtained by a commercially available product or by a known method.

The amount of the cationic polymerizable monomer to be used is appropriately determined according to the structure of the objective fluorine-containing copolymer.

In this production method, by employing living cationic polymerization, it is possible to highly precisely control the number of repeating units derived from the cationic polymerizable monomer.

3.1.3. Lewis Mountain

Examples of the Lewis acid used in the step 1 include a compound represented by the formula (A1) described later and a compound represented by the formula (A2) described later.

AlY ¹ Y ² Y ³ (Al)

(Y ¹ , Y ² and Y ³ in the formula each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group)

&Lt; / RTI >

Examples of the "halogen atom" represented by Y ¹ , Y ² and Y ³ include chlorine, bromine and iodine.

The "alkyl group" represented by Y ¹ , Y ² and Y ³ includes, for example, an alkyl group having 1 to 10 carbon atoms.

The "aryl group" represented by Y ¹ , Y ² and Y ³ includes, for example, an aryl group having 6 to 10 carbon atoms.

The "alkoxy group" represented by Y ¹ , Y ² and Y ³ includes, for example, an alkoxy group having 1 to 10 carbon atoms.

The "aryloxy group" represented by Y ¹ , Y ² and Y ³ includes, for example, an aryloxy group having 6 to 10 carbon atoms.

Specific examples of the aluminum compound represented by the formula (A1) include diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum fluoride, diethyl aluminum iodide, diisopropyl aluminum chloride, diisopropyl aluminum But are not limited to, bromide, diisopropyl aluminum fluoride, diisopropyl aluminum iodide, dimethyl aluminum sesquichloride, methyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, Butyl aluminum dichloride, octyl aluminum dichloride, ethoxy aluminum dichloride, vinyl aluminum dichloride, phenyl aluminum dichloride, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, aluminum trichloride , Aluminum tribromide, ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like, and

Di (2, 6-di-t-butylphenoxy) methyl aluminum, bis (2,4,6-tri-t-butylphenoxy) Alkyl-substituted allyloxy) alkyl aluminum, and the like. These aluminum compounds may be used alone or in combination of two or more.

MZ ¹ Z ² Z ³ Z ⁴ (A2)

(Of formula M represents a tetravalent Ti or ^{Sn. Z 1, Z 2,} Z 3 and Z ⁴ are, each represents a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group)

Wherein each of the tetravalent titanium or tetravalent tin compound is represented by the following formula:

Z ^1, Z ^2, Z ^3, and, "halogen atom" which is represented by a single bar of Z ^4, as the "alkyl", "aryl", "alkoxy" and "aryloxy", each of Y ^1, Y ² and Y ³ are the same as those exemplified above.

Specific examples of the tetravalent titanium compound represented by the formula (A2) include titanium halides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide;

Titanium halide alkoxides such as titanium triethoxy chloride and titanium tri-n-butoxide chloride; And

And titanium alkoxides such as titanium tetraethoxide and titanium n-butoxide.

Specific examples of the tetravalent tin compound represented by the formula (A2) include tin halides such as tin tetrachloride, tin tetrabromide and tin iodide.

These tetravalent titanium compounds and tetravalent tin compounds may be used singly or in combination of two or more.

Examples of the Lewis acid include Fe, Ga, In, Zr, Zr, Hf, Bi, Si, Ge, ), Or a halide of antimony (Sb); Onium salts (e.g., ammonium salts, phosphonium salts); Metal oxides (e.g., Fe ₂ O ₃ , Fe ₃ O ₄ , In ₂ O ₃ , Ga ₂ O ₃ , ZnO, and Co ₃ O ₄ ).

The amount of the Lewis acid used is preferably such that the cationic polymerizable monomer / Lewis acid (molar ratio) is 2 to 1000, more preferably 10 to 1,000.

3.1.4. Growth Stabilizer

In Step 1, an oxygen-containing or nitrogen-containing compound may be used for the purpose of stabilizing growth species in living cationic polymerization.

Here, the term "growth medium" means an active species (cation) present at the end of the polymer in the elongation.

Examples of the oxygen-containing or nitrogen-containing compound include esters, ethers, ketones, imides, phosphoric acid compounds, pyridine derivatives and amines. Specific examples of the esters include esters such as ethyl acetate, butyl acetate, phenyl acetate, methyl chloroacetate, methyl dichloroacetate, ethyl butyrate, ethyl stearate, ethyl benzoate, phenyl benzoate, diethyl phthalate and diethyl isophthalate. .

As the ether, for example, chain ethers such as diethyl ether and ethylene glycol; And cyclic ethers such as dioxane and tetrahydrofuran. Examples of the ketone include acetone and methyl ethyl ketone.

As the imide, for example, ethyl phthalimide can be mentioned.

As the phosphate compound, for example, triethyl phosphate can be mentioned.

As the pyridine derivative, for example, 2,6-dimethylpyridine can be mentioned.

As the amine, for example, tributylamine can be mentioned.

These compounds may be used singly or in combination of two or more kinds.

The amount of the oxygen-containing or nitrogen-containing compound to be used is preferably 0.1 to 2,000 moles, more preferably 1 to 2,000 moles, per 1 mole of the Lewis acid.

The reaction may be carried out in bulk, but preferably a solvent is used.

Examples of the solvent include aliphatic hydrocarbons such as n-pentane, n-hexane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and dichloroethane; And ethers such as dimethyl ether. Nonpolar solvents are particularly preferred. These solvents may be used singly or in combination of two or more kinds.

The solvent is usually used in a solvent: vinyl compound (volume ratio) = 1: 1 to 100: 1, preferably 5: 1 to 30: 1.

The reaction temperature is usually -80 ° C to 150 ° C, preferably -78 ° C to 80 ° C.

The reaction time is usually 1 minute to 1 month, preferably 1 minute to 100 hours.

3.2. Step 2

3.2.1. Cationic polymerization terminator

The " cationic polymerization terminator " used in Step 2 is a compound represented by the formula: R ^c -X ^c -H (wherein the symbols have the same meanings as defined above)

&Lt; / RTI >

When R ^c is a hydrogen atom, the cationic polymerization terminator is preferably water.

When R ^c is an organic group not containing a curable part, the cationic polymerization terminator is preferably an alkanol represented by the formula: R-OH (R in the formula is an alkyl group), more preferably a methyl group.

When R < ^c > is an organic group containing a curable part, the preferable curable part differs depending on the material to be coated, and therefore the preferable cation polymerization stopping system also differs depending on the material.

When the material to be coated is an amorphous synthetic resin (e.g., an acrylic resin), the cationic polymerization terminator is preferably a reducing agent, LiBH ₄ or alkyl alcohol, more preferably methanol.

On the other hand, when the material to be coated is free, the cationic polymerization terminator is preferably represented by the formula: HX ^c -L ^s -R ^cs

(X ^c represents -O-, -S-, -NH-, or a single bond, preferably -O- or -NH- L ^s represents a linker Preferably - (CH ₂ ) n ₈ - (n8 is 1 to 6), more preferably - (CH ₂ ) ₃ - R ^cs represents a silane coupling group)

, More preferably NH ₂ - (CH ₂ ) ₃ -Si (-OEt) ₃ .

The amount of the cationic polymerization terminator used should be such that the reaction terminus of the terminator and the polymer can sufficiently come into contact in the reaction solution, and the amount to be used is not strictly defined.

It is usually 0.01 to 10 times the volume of the reaction solvent, and preferably 0.1 to 1 times the volume of the reaction solvent.

3.3. Other processes

The fluorine-containing copolymer of the present invention thus obtained can be purified by a conventional method, if necessary.

The fluorine-containing copolymer of the present invention produced by such a production method has a high uniformity of molecular weight, for example, a dispersion degree (weight average molecular weight / number average molecular weight) of about 2.5 to 1.0.

4. Oil repellent and / or water repellent coatings

The oil repellent and / or water repellent coating agent of the present invention contains the fluorine-containing copolymer of the present invention.

The oil repellent and / or water repellent coating agent of the present invention may contain the fluorine-containing copolymer of the present invention as a main component or an effective component. Here, the " main component " means a component in which the content in the oil repellent and / or water repellent coating agent exceeds 50% by weight. Refers to a component that remains on the surface-treated substrate to form a film (surface-treated layer), and is capable of exhibiting the effects of the present invention (water repellency, oil repellency, antifouling property, surface slipperiness, friction durability, etc.) it means.

The fluorine-containing copolymer of the present invention can impart oil repellency to the surface of the object by forming a coating on the surface of the object. Further, the fluorine-containing copolymer of the present invention can impart water repellency to the surface of the object by forming a coating on the surface of the object. Therefore, the oil repellent and / or water repellent coating agent of the present invention is used for surface coating of objects for the purpose of water repellent, oil repellent, antifouling, and / or prevention of fingerprint adhesion.

The composition of the oil repellent and / or water repellent coating agent (or the surface treatment composition) of the present invention can be suitably determined according to a desired function.

The oil repellent and / or water repellent coating agent of the present invention may contain, in addition to the fluorine-containing copolymer of the present invention, a fluoropolyether compound, preferably a perfluoropolyether compound, which can be understood as a fluorine-containing oil (Hereinafter sometimes referred to as " fluorine-containing oil " for the purpose of distinguishing it from the fluorine-containing copolymer of the present invention). The fluorine-containing oil does not have a moiety reactive with the substrate (for example, a silyl group). The fluorine-containing oil contributes to improvement of the surface slipperiness of the obtained coating film.

In the oil repellent and / or water repellent coating agent, the fluorine-containing oil per 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more kinds thereof, the total amount thereof and the following also applies) Part, preferably 50 to 200 parts by mass.

Examples of such a fluorine-containing oil include a compound represented by the following formula (2) (perfluoropolyether compound).

R ²¹ - (OC _r F _2r ) _n --OR ²² - (2)

In the formulas, R ²¹ and R ²² each independently represent a perfluoroalkyl group having 1 to 16 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

r is, independently at each occurrence, an integer of 1 to 3 in each occurrence.

The moiety represented by the formula: - (OC _r F _2r ) _nd - includes at least one constituent unit selected from the group consisting of OC ₃ F ₆ , OC ₂ F ₄ and OCF ₂ . That is, the _{formula: - (C r F 2r O} ) nd - part represented by the _{formula: - (OC 3 F 6)} a '- (OC 2 F 4) b' - (OCF 2) c '- expressed in do.

Here, a ', b' and c 'represent the respective repeating number of perfluoropolyethers constituting the main skeleton of the polymer, and are independently integers of 0 to 300, and a', b 'and c' That is, nd is at least 1, preferably from 1 to 100. [

In the present specification, the order of existence of repeating units in adjoining plural round parentheses with subscripts representing the number of repeats is arbitrary. That is, the combination mode of the repeat units may be random or block. Of these repeating units, - (OC ₃ F ₆ ) - represents a repeating unit selected from the group consisting of - (OCF ₂ CF ₂ CF ₂ ) -, OCF (CF ₃ ) CF ₂ - and OCF ₂ CF (CF ₃ ) And is preferably - (OCF ₂ CF ₂ CF ₂ ) -. - (OC ₂ F ₄ ) - can be any of - (OCF ₂ CF ₂ ) - and - (OCF (CF ₃ )) -, preferably - (OCF ₂ CF ₂ ) -.

Examples of the perfluoropolyether compound represented by the formula (2) include compounds represented by any one of the following formulas (2a), (2b) and (2c).

R ²¹ - (OCFCFCF) _a -OR ²² (2a)

R ²¹ - (OCF ₂ CF ₂ ) _{b "} - (OCF ₂ ) _c" -OR ²² (2b)

R ²¹ - (OCF (CF ₃ ) CF ₂ ) _{d "} -OR ²² (2c)

In the formulas, R ²¹ and R ²² are as defined above, a "is an integer of 1 to 100, b" and c "are each independently an integer of 1 or more and 300 or less, and d"Lt; / RTI >

The compound represented by formula (2a) and the compound represented by formula (2b) may be used alone or in combination. When these are used in combination, it is preferable to use the compound represented by formula (2a) and the compound represented by formula (2b) in a mass ratio of 1: 1 to 1:30. According to such a mass ratio, a film excellent in balance between surface slip and friction durability can be obtained.

The fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000. Thereby, the coating film formed by the oil repellent and / or water repellent coating agent of the present invention (the surface treatment layer of the article coated with oil repellent and / or water repellent coating agent of the present invention) can have a high surface slip property. Typically, the compound represented by the formula (2a) preferably has a number average molecular weight of 2000 to 6000, and in the case of the compound represented by the formula (2b), it has a number average molecular weight of 8000 to 30000 . In the range of the number average molecular weight, a film having a high surface slip property can be obtained.

The oil repellent and / or water repellent coating agent of the present invention may contain, in addition to the fluorine-containing copolymer of the present invention, a silicone compound (hereinafter referred to as "silicone oil") which can be understood as a silicone oil. Silicone oil contributes to improvement of the surface slip property.

The silicone oil may be contained in, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the perfluoropolyether group-containing silane compound in the oil repellent and / or water repellent coating agent.

As such a silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2000 or less can be used. The straight-chain silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with an alkyl, an aralkyl, a polyether, a higher fatty acid ester, a fluoroalkyl, an amino, an epoxy, a carboxyl, an alcohol or the like. The cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil and the like.

The formation of the film by the oil repellent and / or water repellent coating agent of the present invention can be carried out by, for example, coating a solution obtained by dissolving the oil repellent and / or water repellent coating agent in a solvent in a solvent such as a roll coating method, a gravure coating method, a microgravure coating method, Is applied to the surface of the object by a conventional method such as a coating method, a bar coating method, a spray coating method, a die coating method, a spin coating method, a dip coating method, or a vapor deposition method and dried, .

When the hardness of the coating film is required or when the curing rate is to be improved, monofunctional and polyfunctional (meth) acrylate monomers may be suitably added for the purpose of improving adhesion to the base. Since the fluorine-containing copolymer of the present invention exhibits high compatibility with the monofunctional and polyfunctional (meth) acrylate monomers, the added monomers function as a crosslinking agent without deteriorating the appearance and have a hardness suitable for the cured film, The adhesion of the base material and the curing speed are improved.

The fluorine-containing copolymer of the present invention exhibits high solubility not only in a fluorine-containing organic solvent but also in a fluorine-free organic solvent as a general solvent. Therefore, the fluorine-containing copolymer is dissolved in a fluorine-containing organic solvent or a fluorine- It can be applied to the surface.

Examples of such fluorine-containing organic solvents include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoro Perfluorobutyl tetrahydrofuran, hydrofluoroether (Nobeq (trade name), HFE-7100 and the like), perfluoroalkyl bromide, perfluoroalkyl bromide, perfluoroalkyl bromide, (Perfluoroalkyl) ethyl methacrylate, acrylic acid 2- (perfluoroalkyl) ethyl acrylate, perfluoropolyethers such as perfluoro polyether (trade name, Dendum (trade name) Fluoroalkyl) ethyl, perfluoroalkylethylene, Freon 134a and hexafluoropropene oligomers.

Examples of the fluorine-free organic solvent include methyl isobutyl ketone, propylene glycol monomethyl ether, pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene , Acetone, 2-butanone, acetonitrile, benzonitrile, butanol, 1- (2-methoxyphenyl) acetonitrile, dimethyl sulfoxide, dimethyl sulfoxide, dimethyl sulfoxide, Propanol, 2-propanol, ethanol, methanol, triethylamine and aniline.

Among them, the solvent for dissolving the fluorine-containing copolymer of the present invention is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, ethyl acetate or 2-propanol.

These solvents may be used singly or in combination of two or more kinds.

The fluorine-containing copolymer of the present invention exhibits high solubility even for a fluorine-free organic solvent which is a general-purpose solvent.

Examples of the material (substrate) of the coating object include inorganic materials such as glass; Polyolefin resins such as polyethylene and polystyrene; Acrylic resins such as polymethyl methacrylate; polyester resins such as polyarylate and polyethylene terephthalate; synthetic resins such as polycarbonate resin and phenol resin; Iron, aluminum, copper, and the like, but are not limited thereto.

Among them, glass or an amorphous synthetic resin (e.g., acrylic resin), a highly heat-resistant cyclic polyolefin resin (COP), a polyester resin (e.g., polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) Polycarbonate resins are preferred.

The fluorine-containing copolymer of the present invention may also be added to a commercially available hard coating agent.

Since the fluorine-containing copolymer of the present invention exhibits high compatibility, it is possible to impart high water repellency and antifouling property to the surface without impairing the physical properties of a commercially available hard coating agent.

The coating formed of the oil repellent and / or water repellent coating agent of the present invention is excellent in water repellency, oil repellency, antifouling property, prevention of fingerprint adhesion and durability, and can be firmly bonded to a coating object and is transparent. The oil repellent and / or water repellent coating agent can be suitably used for coating various articles (products, devices or parts).

The article containing the coating formed from the oil repellent and / or water repellent coating agent of the present invention is also within the scope of the present invention.

Hereinafter, an article having a coating formed from such a oil repellent and / or water repellent coating agent will be described in more detail.

The article of the present invention comprises a substrate and a fluorine-containing copolymer or oil-repellent and / or water-repellent coating agent (hereinafter referred to simply as "oil repellent and / or water repellent coating agent" Layer (surface treatment layer).

Such articles can be produced, for example, as follows.

For example, when the article to be manufactured is an optical member, the substrate may be a material for an optical member, such as glass or transparent plastic. Further, a layer such as a hard coating layer and / or an antireflection layer may be formed on the surface region where the surface treatment layer is formed by the oil repellent and / or water repellent coating agent. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of the mineral available for the anti-reflection _{layer, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O ₃ , SnO ₂ , MgF ₂ , WO ₃ , and the like. These minerals may be used alone or in combination of two or more thereof (for example, as a mixture). In the case of the multilayer antireflection layer, it is preferable to use SiO ₂ and / or SiO _{2 as} the outermost layer. When an article to be manufactured is an optical glass part for a touch panel, a transparent electrode, for example, a thin film made of indium tin oxide (ITO) or indium zinc oxide may be provided on a part of the surface of a substrate (glass) . The substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), a fogging film layer, a hard coating layer, a polarizing film, a retardation film and a liquid crystal display module do.

The shape of the substrate is not particularly limited. The surface area of the substrate on which the surface treatment layer is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined in accordance with the use of the article to be produced, the specific specification, and the like.

Such a base material may be one having a hydroxyl group originally in its surface portion. Examples of such a material include glass (metal) (particularly, non-metal) on which a natural oxide film or a thermally oxidized film is formed, ceramics, and semiconductors. Alternatively, in the case where it is not sufficient to have a hydroxyl group, such as a resin, or in the case where the hydroxyl group is not originally possessed, a hydroxyl group can be introduced or increased on the surface of the substrate by carrying out a suitable pretreatment to the substrate. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can be suitably used for introducing or increasing a hydroxyl group on the surface of the substrate and for purifying the substrate surface (removing foreign matter or the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bonding group is formed in advance in the form of a monomolecular film on the surface of a substrate by the LB method (Langmuir-Blodgett method) or a chemisorption method, and then oxygen or nitrogen And cleaving an unsaturated bond under an atmosphere containing the compound.

In addition, or as such a substrate, there may be used a substance having a different reactive group (e.g., Si-H group) on its surface portion. Examples thereof include a silicon compound having at least one Si-H group or a substrate formed of a material containing an alkoxysilane.

Subsequently, a film of the above oil repellent and / or water repellent coating agent is formed on the surface of such a base material, and this film is optionally post-treated to form a surface treatment layer.

The film formation of the oil repellent and / or water repellent coating agent can be carried out by applying the oil repellent and / or water repellent coating agent described above to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Examples of the wet coating method include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like methods.

Examples of the dry coating method include vacuum vapor deposition, sputtering, CVD, and similar methods. Specific examples of the vacuum deposition method include resistance heating, electron beam, high frequency heating, ion beam, and similar methods. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and the like.

It is also possible to coat by an atmospheric pressure plasma method.

When the wet coating method is used, the oil repellent and / or water repellent coating agent can be applied to the substrate surface after being diluted with a solvent. In view of the stability of the oil repellent and / or water repellent coating agent and the volatility of the solvent, the following solvents are preferably used: perfluoro aliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethyl Cyclohexane and perfluoro-1,3-dimethylcyclohexane); Polyfluoroaromatic hydrocarbons (e. G., Bis (trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbons; (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl ethyl ether (Perfluoroalkyl groups and alkyl groups such as ₄ F ₉ OC ₂ H ₅ ) and perfluorohexylmethyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) . These solvents may be used singly or as a mixture of two or more thereof. Among them, hydrofluoroethane is preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) are particularly preferable.

Hereinafter, the case where the fluorine-containing copolymer of the present invention used in the oil repellent and / or water repellent coating agent of the present invention has a silane coupling group will be described in more detail.

The film formation is preferably carried out so that the oil-repellent and / or water-repellent coating agent in the film is present together with the catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of the wet coating method, the catalyst may be added to the diluent of the oil repellent and / or water repellent coating agent immediately before the oil repellent and / or water repellent coating agent is diluted with the solvent and then applied to the surface of the substrate. In the case of the dry coating method, the oil-repellent and / or water-repellent coating agent added with the catalyst is directly subjected to vacuum evaporation treatment, or the metal porous article such as iron or copper is impregnated with a catalytic oil-repellent and / A vacuum deposition process may be performed using a material.

For the catalyst, any suitable acid or base may be used. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. As the base catalyst, for example, ammonia, organic amines and the like can be used.

Then, if necessary, the film is post-treated. This post-treatment is not particularly limited, and for example, water supply and dry heating may be carried out in order, and more specifically, the following treatment may be carried out.

After the oil repellent and / or water repellent coating agent is formed on the surface of the substrate as described above, moisture is supplied to the film (hereinafter also referred to as " precursor film "). The method of supplying moisture is not particularly limited, and for example, a method such as condensation due to a temperature difference between the precursor film (and substrate) and the ambient atmosphere, or spraying of water vapor (steam) may be used.

When water is supplied to the precursor film, it is considered that water can act on the silane coupling group in the fluorine-containing copolymer of the present invention to hydrolyze it.

The supply of water can be carried out, for example, at 0 to 500 ° C, preferably at 100 ° C or more, and at an atmosphere of 300 ° C or less. By supplying water in this temperature range, hydrolysis can proceed. The pressure at this time is not particularly limited, but can be easily set at normal pressure.

Subsequently, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 캜. The drying and heating method is not particularly limited and the precursor film together with the base material may have a temperature exceeding 60 캜, preferably exceeding 100 캜, for example, a temperature of 500 캜 or lower, preferably 300 캜 or lower, It may be disposed under an atmosphere of unsaturated water vapor pressure. The pressure at this time is not particularly limited, but can be easily set at normal pressure.

Under such an atmosphere, the silane coupling groups after the hydrolysis are rapidly dehydrated and condensed between the fluorine-containing copolymers of the present invention. Further, between the compound and the substrate, the silane coupling group after hydrolysis of the compound rapidly reacts with the reactive group present on the surface of the substrate, and when the reactive group present on the surface of the substrate is a hydroxyl group, dehydration and condensation are carried out. As a result, when a bond is formed between the fluorine-containing copolymers of the present invention and the fluorine-containing copolymer (A) of the present invention is used, A bond is also formed between the coalescents and the substrate.

The above-described water supply and drying heating may be performed continuously by using superheated water vapor.

The superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point. Under superatmospheric pressure, the superheated steam is a gas having a temperature exceeding 100 캜, generally not higher than 500 캜, for example, not higher than 300 캜, It is a gas that has become unsaturated steam pressure by heating to a temperature. When the substrate on which the precursor film is formed is exposed to superheated water vapor, condensation occurs on the surface of the precursor film due to the difference in temperature between the superheated water vapor and the relatively low temperature precursor film, whereby water is supplied to the precursor film . As the temperature difference between the superheated steam and the precursor film becomes shorter, the moisture on the surface of the precursor film evaporates in a dry atmosphere by superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the moisture content of the precursor film surface is lowered, that is, while the precursor film is under a dry atmosphere, the surface precursor film of the substrate is heated to a temperature of the superheated water vapor (a temperature exceeding 100 캜 under atmospheric pressure) do. Therefore, when superheated water vapor is used, water supply and dry heating can be continuously performed only by exposing the substrate on which the precursor film is formed to overheated water vapor.

The post-treatment can be carried out as described above. It should be noted that such a post-treatment can be carried out to further improve the friction durability but is not essential to the production of the article of the present invention. For example, the oil-repellent and / or water-repellent coating agent may be applied to the surface of the base material and then left as it is.

As described above, the surface treatment layer derived from the film of the oil repellent and / or water repellent coating agent is formed on the surface of the base material to produce the article of the present invention. The surface treatment layer thus obtained is excellent in water repellency, oil repellency, antifouling property (for example, preventing adhesion of contamination such as fingerprints), surface slip property (or lubricity, ), Friction durability, and the like, and can be suitably used as a functional thin film.

That is, the present invention also relates to an optical material having the cured product in the outermost layer.

As the optical material, various optical materials in addition to the optical materials related to displays and the like as exemplified later can be preferably used.

Examples include cathode ray tubes (CRTs, e.g., televisions, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD) Field Emission Display), or a protective plate of a display of such a display, or a surface of the protection plate treated with an antireflection film.

The article having the surface treatment layer thus obtained is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as glasses; PDP, LCD, etc., anti-reflective plate, polarizer plate, anti-glare plate; A touch panel sheet of a device such as a cellular phone, a portable information terminal, and the like; A disc surface of an optical disc such as a Blu-ray disc, a DVD disc, a CD-R, or an MO; Optical fiber and so on.

The thickness of the surface treatment layer is not particularly limited. In the case of the optical member, the surface treatment layer preferably has a thickness of 1 to 30 nm, preferably 1 to 15 nm, in view of optical performance, surface slipperiness, friction durability and antifouling property.

The products obtained by using the oil repellent and / or water repellent coating agent of the present invention have been described in detail above. The use of the oil repellent and / or water repellent coating agent of the present invention, the method of use, and the method of manufacturing the article are not limited to those exemplified above.

Example

The symbols in the examples are used in the following meaning.

s: singlet

t: triplet

TLC: Thin layer chromatography

TMS: tetramethylsilane

THF: tetrahydrofuran

Me: methyl group

Et: ethyl group

MIBK: methyl isobutyl ketone

MEK: methyl ethyl ketone

MOVE: 2-methoxyethyl vinyl ether [the formula: CH ₂ = CH-O- (CH ₂ ) ₂ -O-CH ₃ ]

AcVE: 2- (vinyloxy) ethyl acrylate [rational _{formula: CH 2 = CH-O- (} CH 2) 2 -O-CO-CH = CH 2]

AcVEE: 2- (vinyloxy) ethoxy-ethyl acrylate in the rational _{formula: CH 2 = CH-O- (} CH 2) 2 -O- (CH 2) 2 -O-CO-CH = CH 2]

McVE: 2- (vinyloxy) ethyl methacrylate [rational _{formula: CH 2 = CH-O- (} CH 2) 2 -O-CO-C (-CH 3) = CH 2]

McVEE: ethyl 2- (vinyloxy) methacrylate [rational _{formula: CH 2 = CH-O- (} CH 2) 2 -O- (CH 2) 2 -O-CO-C (-CH 3) = CH ₂ ]

IBVE: isobutyl vinyl ether [rational _{formula: CH 2 = CH-O-} CH 2 -CH (-CH 3) 2]

5FVE: 3- (perfluoro-ethyl) propoxy vinyl ether [rational _{formula: CH 2 = CH-O- (} CH 2) 2 -O- (CH 2) 3 -C 2 F 5]

PFPE (group): F- (CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (when PFPE is univalent), or

-CF ₂ -CF ₂ -O- (CF ₂ -CF ₂ -CF ₂ -O) _n -CF ₂ -CF ₂ - (when PFPE is divalent)

(N in the formula represents the number of repeats)

PFPE-Z _{(group): -CF 2 - (OCF 2} ) m - (OCF 2 CF 2) n -OCF 2 - ( circles indicate respectively the number of iterations m, and n in the formula)

PFPE-Z-diol: HOCH ₂ -CF ₂ - (OCF ₂ ) _m - (OCF ₂ CF ₂ ) _n -OCF ₂ -CH ₂ -OH (m and n each independently represent the number of repeating units)

As HCFC-225, AK-225 (trade name, Asahi Glass) was used.

Synthetic example One

Synthesis of 2- [3-poly (perfluoropropyloxy) -2,2,3,3-tetrafluoropropoxy] ethoxyvinyl ether

60 g (15 mmol) of an alcohol (perfluoropolyether group-containing alcohol having a number average molecular weight of 4000, Daikin Kogyo Co., Ltd.) represented by the following chemical formula: PFPE-CH ₂ OH, 3.5 g (103 mmol) of tetrabutylammonium, 120 mL of a 40% aqueous sodium hydroxide solution and 250 mL of m-hexafluorooxylene were placed, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To the mixture was added 120 mL of 2-chloroethyl vinyl ether, and a dimox cooler was attached to an eggplant type flask. The mixture was stirred at 70 캜 for 48 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled off with a solvent in an evaporator until it was almost completely dried. The remaining reactants were dissolved in a fluorine-based inert liquid (Fluorinert FC-72, Sumitomo 3M Co.). The solution was extracted three times with dichloromethane to remove the co-product. Here, the removal of the coalescence was judged by checking the extract with TLC (developing solvent: HCFC-225, detection method: spraying and heating of potassium permanganate solution, judgment standard: spot disappearance at the origin). The solvent was distilled off under reduced pressure to obtain the desired 2- [3-poly (perfluoropropyloxy) -2,2,3,3-tetrafluoropropoxy] ethyl vinyl ether.

The structure of the target substance was confirmed by NMR spectrum.

NMR spectrum was measured by JEOL model JNM-ECS400 (measurement solvent: CDCl ₃ - benzene (1 hexafluoropropane: 5)).

In chemical shift, TMS was used for ¹ H-NMR and CFCl ₃ was used for ¹⁹ F-NMR, and the author's long side was positive.

^{_{1 H-NMR (CDCl 3 -C}} 6 F 6): δ 3.86-3.91 (2H, m), 3.91-3.96 (3H, m), 4.08 (2H, t, J = 13.5 Hz), 4.13 (1H, dd , J = 14.7, 1.8 Hz), 6.40 (1H, dd, J = 14.7, 6.6 Hz).

^{_{19 F-NMR (CDCl 3 -C}} 6 F 6): δ -83.12 (s), -84.27 (s), -84.52 (s), -84.82 (s), -85.06 (s), -85.50 (s) , -87.36 (t, J = 12.5 Hz), -125.65 (t, J = 13.5 Hz), -130.61 (s), -130.69 (s), -130.79 (s), -131.57 (s).

The peak of the CF ₂ group (triplet peak at -128.33 ppm) at the? -Position of the starting alcohol disappeared and the triplet peak at -125.65 ppm was detected, confirming the formation of the ether group.

Hereinafter, this 2- [3-poly (perfluoropropyloxy) -2,2,3,3-tetrafluoropropoxy] ethyl vinyl ether is abbreviated as PFPE4000VE.

Synthetic example 2

Synthesis of PFPE group-containing cationic polymerization initiator (1)

All the glass apparatuses for synthesis and polymerization were dried for 3 hours in a blower constant temperature drier (130 ° C).

The glass reaction vessels A and B each equipped with a three-way valve were each heated under a nitrogen gas stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen and sufficiently dried in the vessel.

In a dry nitrogen atmosphere, 19.7 mL of HCFC-225 and 0.3 mL (4 mmol) of trifluoroacetic acid were placed in a vessel A and stirred well to obtain 20 mL (200 mol / l) of Solution A. 5.9 mL of HCFC-225 and 4.1 mL (2 mmol) of PFPE4000VE were added to a separate glass vessel B and stirred well to obtain 10 mL (200 mol / l) of solution B. The diluted solutions A and B were each cooled in an ice water bath at 0 캜 for about 15 minutes and the cooled solution A was added slowly to the solution B with nitrogen flow for about 5 minutes and then stirred for 10 minutes to obtain a PFPE Containing cationic polymerization initiator. (Quantity: 19.5 ml, yield: 99.5% or more)

Hereinafter, this PFPE group-containing cationic polymerization initiator may be abbreviated as PFPE4000VETFA.

When preserving PFPE4000VETFA, the purified PFPE4000VETFA was diluted to 0.1 M with HCFC-225, and was melted in a brown glass ampoule under dry nitrogen and stored in a cool dark place.

Synthetic example 3

Synthesis of PFPE group-containing cationic polymerization initiator (2)

4.1 mL (2 mmol) of PFPE4000VE was diluted with HCFC-225 in a glass reaction vessel equipped with an Allyn condenser and a three-way valve to make a total of 10 mL. Thereto, 11 mL (200 mmol) of acetic acid and a small amount of hydrochloric acid were added, and the mixture was reacted at 50 DEG C for 6 hours. The obtained crude product was distilled under reduced pressure at 60 占 폚 or lower, and then dried under reduced pressure with stirring for 10 hours or more to obtain a product (cationic polymerization initiator) which is a colorless transparent liquid. (Quantity: 19.5 ml, yield: 99.5% or more)

Thereafter, this cationic polymerizable initiator may be abbreviated as PFPE4000VEAC.

Synthetic example 4

Synthesis of poly (perfluoropropyloxy) -1, omega -bis (vinyloxyethyl) ether

In a 20 mL eggplant-shaped flask,

₁ g of a diol substance (number average molecular weight 4000, Daikin Kogyo Co., Ltd.) containing perfluoropolyether groups and represented by the following formula: HOCH ₂ -PFPE-CH ₂ OH (wherein n represents a repeating number) 850 mg (2.5 mmol) of tetrabutylammonium hydrogen sulfate, 2 mL of a 40% aqueous solution of sodium hydroxide and 5 mL of m-hexafluoroxylene were placed, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To the mixture was added 2 mL of 2-chloroethyl vinyl ether, and a dimox cooler was attached to an eggplant-shaped flask. The mixture was stirred at 70 캜 for 72 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled off with a solvent in an evaporator until it was almost completely dried. The remaining reactants were dissolved in a fluorine-based inert liquid (Fluorinert FC-72, Sumitomo 3M Co.). This solution was extracted three times with acetone and then with dichloromethane to remove the coagulated matter. Here, the removal of the coalescence was judged by checking the extract with TLC (developing solvent: HCFC-225, detection method: spraying and heating of potassium permanganate solution, judgment standard: spot disappearance at the origin). The solvent was distilled off under reduced pressure to obtain the desired product. (Yield: 650 mg, yield: 63%).

Hereinafter, this compound may be abbreviated as " dimundum diol bisvinyl ether ".

NMR spectra, JEOL model was measured by JNM-ECS400 (measurement solvent: CDCl ₃ - benzene (1 hexafluoropropane: 5)).

^{_{1 H-NMR (CDCl 3 -C}} 6 F 6): δ 3.84-3.98 (5H, m), 4.08 (2H, t, J = 13.5 Hz), 4.10 (1H, dd, J = 14.7, 1.8Hz), 6.39 (1H, dd, J = 14.7, 13.5 Hz).

Synthetic example 5a

Synthesis of PFPE group-containing cationic polymerization initiator (adduct dimol diol bisvinyl ether acetic acid adduct)

218 mg (0.054 mmol) of the above obtained dimndnol diol bisvinyl ether and 10 μL of acetic acid were heated in 90 mL of m-hexafluoroxylene under nitrogen atmosphere at 90 ° C. for 72 hours. The trace of the reaction was confirmed by measuring the vinyl H (CH ₂ = CH-O) observed at 6.4 ppm in ¹ H-NMR and the methine H (-CH (-O-CO-CH ₃ ) - O-CH ₂ -).

After cooling, the solvent was distilled off under reduced pressure to obtain the target product. No further purification was carried out and used in the polymerization.

Diphenol diol bisvinyl ether acetic acid adduct

^{_{1 H-NMR (CDCl 3 -C}} 6 F 6): δ 1.40 (3H, d, J = 5.1 Hz), 2.07 (3H, s), 3.73-3.92 (4H, m), 4.03 (2H, t, J = 13.2 Hz), 5.94 (1H, q, J = 5.1 Hz).

Synthetic example 5b

Synthesis of 2- [3-poly (perfluoropropyloxy) -2,2,3,3-tetrafluoropropoxy] vinyl ether

Ishii et al. Synthesized the target compound by applying the method described in Journal of American Chemical Society, 2002, vol. 124, p. 1590 (American Chemical Society).

(1 mmol) of PFPE-CH2OH (DEMNUM SA (number average molecular weight 4000), Daiking Kogyo), 276 μL (3 mmol) of vinyl acetate, 106 mg (1 mmol) of sodium carbonate, A suspension of 4 ml of m-hexafluoroxylene of 22 mg (0.03 mmol) of chlorobis (1,5-cyclooctadiene) 2 iridium (I) complex ({IrCl (COD)} ₂ ) Respectively.

After the solvent was distilled off, the reaction product was purified by column chromatography (developing solvent: AK-225) using triethylamine treatment (1 hour stirring in 1% hexane and then drying) using silica gel to obtain the desired product (quantitative) .

^{_{1 H-NMR (C 6 F}} 6): δ 3.80 (2H, t, J = 12.4 Hz), 3.82 (1H, dd, J = 2.7, 6.4Hz), 3.96 (1H, dd, J = 2.7, 14.2Hz ), 6.10 (1H, dd, J = 6.4, 14.2 Hz).

In addition, in the ¹⁹ F-NMR measurement, the peak of the CF ₂ group (triplet peak at -128.33 ppm) at the? -Position of the starting alcohol disappeared and the triplet peak at -124.99 ppm was detected, .

Synthetic example 5c

The polymerization initiator 5c shown in the above formula was prepared by the same method as in Synthesis Example 2 using the compound obtained in Synthesis Example 5b. The reaction was followed by disappearance of 6.10 ppm of olefin H in ¹ H-NMR and confirmation of methine H derived from acetal at 5.90 ppm.

Synthetic example 6

Synthesis of Vinyl Ether Having Silane Coupling Group as Curable Part (1)

According to the method described in Crivello, J. V., Mao, Z., Chemistry of Materials, 1997, Vol. 9, p. 1554 (American Chemical Society), a target product was synthesized.

200 mg), triethoxysilane (32.8 g, 200 mmol), and Rh (I) Cl (PPh ₃ ) ₃ (30 mg, 0.03 mmol) were added to a solution of 1- (1-propenoxy) -2- (vinyloxy) ) In toluene (50 mL) was stirred under reflux for 72 hours. After cooling, the solvent was distilled off under reduced pressure, and the intended product was obtained by distillation (yield: 25.0 g, yield: 43%). Boiling point: 95 캜 (100 Pa)

1- (1-Propenoxy) -2- (2-triethoxysiloxyethoxy) ethane

¹ H-NMR (CDCl ₃ ):? 1.02-1.10 (2H, m), 1.16-1.23 (9H, m), 1.49-1.56 (3H, m), 3.54-3.62 (1H, d, J = 6.9, 2.3 Hz), 4.29-4.43 (cis vinyl H, m), 4.68-4.81 (trans vinyl Dd, J = 4.6, 1.8 Hz), 6.22 (trans vinyl H, dq, J = 12.4, 1.4 Hz), 6.46 (1H, dd, J = 14.2, 6.9 Hz), 5.94 (cis vinyl H, .

Synthetic example 7a

Synthesis of Vinyl Ether Having Silane Coupling Group as Curable Part (2)

To a dry anhydrous dichloromethane solution (30 mL) of 2-vinyloxyethanol (3.56 g, 40 mmol) and triethylamine (4.09 g, 40 mmol) was added a solution of 3- (triethoxysilyl) propyl isocyanate (10 g, 40 mmol) An anhydrous dichloromethane solution (10 mL) was added dropwise. After the reaction solution was stirred at room temperature for 20 hours, the solvent was distilled off under reduced pressure, and further distilled under reduced pressure to obtain the target product (yield: 8.5 g, yield: 63%). Boiling point: 150 ° C (100 Pa)

^{_{1 H-NMR (CDCl 3)}} : δ 0.57-0.64 (2H, m), 1.21 (9H, t, J = 6.9 Hz), 1.56-1.66 (2H, m), 3.12-3.21 (2H, m), 3.80 (1H, d, J = 6.7, 1.8 Hz), 4.26 (1H, d, J = 6.9 Hz), 3.83-3.89 4.32 (2H, m), 5.02 (1H, bs), 6.43 (1H, dd, J = 14.7, 6.4 Hz).

Example One

Synthesis of Copolymer Containing PFPE and a Curable Part (A-M-B-N Type) (1)

In the type indication of the copolymer, A represents a moiety having a PFPE group. And B represents a block including a constituent unit having a curable part. And M represents a block containing a constituent unit not containing a curable part. And N represents a terminal group which does not contain a curing portion.

The glass apparatuses for synthesis and polymerization were all dried in a air-blowing constant-temperature drier (130 ° C) for 3 hours.

The glass reaction vessel equipped with the three-way valve was heated under nitrogen gas flow, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

2.0 mL (previously diluted with 0.1 mol / L of HCFC-225) (corresponding to 0.2 mmol) of PFPE4000VETFA as a cationic polymerization initiator containing PFPE group, 5.82 mL of HCFC-225 as a polymerization solvent, 1.0 mL of 1,4-dioxane was added as an addition base. Further, 0.18 mL (1.6 mmol) of MOVE as a monomer containing no curable part was added to make 9.0 mL as a whole, and the mixture was cooled to 0 占 폚, stirred with a magnetic stirrer under nitrogen pressure, Lt; 0 > C. To this was added 1 mL (0.2 mmol) of ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) which had been previously diluted with a polymerization solvent HCFC-225 and allowed to stand at 0 캜 to rapidly initiate polymerization under dry nitrogen to initiate polymerization for 3 minutes Thereafter, 0.12 mL (1 mmol) of McVE (0.24 mL as HCFC-225 solution) diluted twice with HCFC-225 as a monomer containing a curable part was added, and after 60 minutes, a methanol (MeOH) solution of 1% ammonia was added To stop the reaction.

By this process, a desired AMBA type copolymer was obtained.

The resulting polymer was purified as follows. First, the reaction solution after the termination of the polymerization was diluted with HCFC-225, and then a small amount of methanol was added to remove the catalyst residue. Six times with 0.6N HCl aqueous solution and three times with ion-exchanged water, Lt; / RTI > This solution was transferred to an eggplant-shaped flask, and the solvent, the unreacted monomer and the added base were distilled off under reduced pressure using a rotary evaporator. After that, it was shaded and stored in a refrigerator.

¹ H-NMR (CDCl ₃ ): δ 0.75-0.95 (m), 1.00-2.10 (m), 2.15-2.40 (m), 3.25-3.40 (m), 3.40-4.00 ), 4.60-4.70 (m), 5.25-5.45 (m), 5.45-5.80 (m), 6.00-6.15 (m).

From the point that the olefin protons derived from methacrylate were observed at 5.45-5.80 ppm and 6.00-6.15 ppm, and the olefin protons derived from vinyl ether were not observed at 4 ppm and 6.5 ppm, the vinyl ether units were cationically polymerized, Methacrylate units remained unreacted. From the above, it was confirmed that a polymer having a desired structure was obtained.

(Mn) and a molecular weight distribution (Mw / Mn) of the polymer were calculated by gel permeation chromatography (GPC) measurement. The molecular weight distribution (Mw / Mn) Respectively. The results are summarized in Table 7.

Further, it was confirmed by NMR measurement that there was no residual polymerization initiator, and it was confirmed that the resulting polymer contained a curable part by the presence of a C = C bond peak based on the (meth) acryl group.

The obtained polymer was subjected to thermal analysis (TGA, DSC). The results are summarized in Table 7.

Further, the resulting polymer was tested for solubility in methyl isobutyl ketone (MIBK), acetone, propylene glycol monomethyl ether (PGME), ethyl acetate, butyl acetate and chloroform.

(Way)

The sample was weighed and measured so that the total solution became 1 g, and the state of the solution after 12 hours at room temperature was visually observed.

The results are shown in Table 8. Symbols in Table 8 indicate the following evaluations.

(evaluation)

○ Transparent and uniformly dissolved.

△ Turbidity was present but dissolved.

X was not dissolved.

Example 2 to 9

Synthesis of Copolymer Containing PFPE and a Curable Part (A-M-B-N Type) (2)

A-M-B-N type copolymer was synthesized by the same procedure as in Example 1 except that the amount and kind of the monomers to be used were changed and cation polymerization was carried out using PFPE4000VETFA as a cationic polymerization initiator.

The amounts and kinds of the monomers used are shown in Table 1.

Various physical properties of the obtained polymer were measured in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 10

Synthesis of Copolymer Containing PFPE Group and Curable Part (A-M / B-N Type)

In the indication of the type of copolymer, A represents a moiety having a PFPE group. B represents a portion containing a curable part. And M / B represents a portion where the constituent unit M containing no curable part and the constituent unit B containing a curable part are randomly copolymerized.

A glass reaction vessel equipped with a three-way valve was heated under nitrogen gas flow, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

2.0 mL (previously diluted with 0.1 mol / L of HCFC-225) (corresponding to 0.2 mmol) of PFPE4000 VETFA as a cationic polymerization initiator containing PFPE group, 5.7 mL of HCFC-225 as a polymerization solvent, 1.0 mL of 1,4-dioxane was added. Further, 0.12 mL (1 mmol) of AcVE diluted twice with HCFC-225 as monomers containing (1) 0.18 mL (1.6 mmol) of MOVE as a monomer containing no curing component and (2) a curable component was added under dry nitrogen The mixture was cooled to 0 占 폚 and stirred under a nitrogen atmosphere with a magnetic stirrer in an ice bath, and then cooled at 0 占 폚. To this was added 1 mL (0.2 mmol) of ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) which had been previously diluted with a polymerization solvent HCFC-225 and kept constantly at 0 ° C under a dry nitrogen to initiate polymerization , And after 60 minutes, a methanol solution of 1% ammonia was added to stop the reaction.

By this process, the desired A-M / B-N type copolymer was obtained.

Purification of the resulting polymer was carried out in the same manner as in Example 1. By NMR measurement, it was confirmed that the resulting polymer contained a curable part by the absence of residual species and the presence of a peak of C = C bond based on an acrylic group.

Various physical properties of the resulting polymer were measured in the same manner as in Example 1.

The results are summarized in Tables 7 and 8.

Example 11

Synthesis of Copolymer Containing PFPE Group and Curable Part (A-B-N Type) (1)

In the indication of the type of copolymer, A represents a moiety having a PFPE group. And B represents a block including a constituent unit having a curable part. And N represents a terminal group having no curable part.

The glass apparatuses for synthesis and polymerization were all dried for 3 hours in a blower constant-temperature drier (130 ° C).

The glass reaction vessel equipped with the three-way valve was heated under a nitrogen gas stream, cooled to room temperature under nitrogen pressure, returned to normal pressure with dry nitrogen, and sufficiently dried in the vessel.

2.0 mL (previously diluted with 0.1 mol / L of HCFC-225) (corresponding to 0.2 mmol) of PFPE4000VETFA as a cationic polymerization initiator containing PFPE group, 5.88 mL of HCFC-225 as a polymerization solvent, 1.0 mL of 1,4-dioxane was added. As a monomer containing a curable part, 0.12 mL (1 mmol) of AcVE diluted with HCFC-225 (0.24 mL as HCFC-225 solution) was added under dry nitrogen to make 9.0 mL of the whole, After stirring, the mixture was stirred under a nitrogen pressure and in an ice bath using a magnetic stirrer and allowed to stand at 0 ° C. On the other hand, diluted with HCFC-225 in a polymerization solvent in advance, and the ethyl aluminum sesquichloride (Et ₁ _.5 AlCl ₁ _.5) of the screen which had a constant temperature to 0 ℃, 1mL (0.2mmol) was added quickly in dry nitrogen Polymerization was initiated.

After 60 minutes, the reaction was stopped by adding a methanol solution of 1% ammonia.

By this process, a desired AB-N type copolymer was obtained.

The results are summarized in Tables 7 and 8.

Example 12 to 17

Synthesis of Copolymer Containing PFPE Group and Curable Part (A-B-N Type) (2)

A-B-N type copolymer was synthesized by cation polymerization using PFPE4000 VETFA as a polymerization initiator by changing the amount of monomers to be used in the same procedure as in Example 11.

The amounts and kinds of monomers used and the like are shown in Table 2.

The resulting polymer was measured for various physical properties in the same manner as in Example 1. The results are summarized in Tables 7 and 8.

Example 18

Synthesis of Copolymer (A-M-C Type) Containing PFPE Group and Curable Part (1)

In the indication of the type of copolymer, A represents a moiety having a PFPE group. And M represents a block containing a constituent unit not containing a curable part. And C represents a terminal group containing a curable part.

2.0 mL (previously diluted with 0.1 mol / L of HCFC-225) (corresponding to 0.2 mmol) of PFPE4000VETFA as a PFPE-containing cationic polymerization initiator, 5.70 mL of HCFC-225 as a polymerization solvent, , And 1.0 mL of 4-dioxane was added. Further, 0.3 mL (2.6 mmol) of MOVE as a monomer having no curable part was added under dry nitrogen to make 9.0 mL as a whole, and the mixture was cooled to 0 占 폚. Then, using a magnetic stirrer under nitrogen pressure and in an ice bath, And was cooled at 0 ° C. After 3 minutes, the reaction mixture was rapidly transferred to a low-temperature bath at -30 ° C. and reacted for 60 minutes. Then, ₂ mL of a mixed solution of NH ₂ - (CH ₂ ) ₃ -Si (-OEt) ₃ : THF Was added to stop the reaction.

The resulting polymer was purified as follows. First, the reaction solution after the termination of the polymerization was diluted with HCFC-225, and dialyzed in a methanol solution for 3 days using a dialysis membrane having a molecular weight size of 6000 to remove the catalyst residue, the unreacted monomer and the added base. The obtained polymer was stored as a 20% HCFC-225 solution so as not to be in contact with water.

From the NMR measurement, it was confirmed that no residual species remained, and from the presence of the ethyl group of the triethoxysilyl group, it was confirmed that the resulting polymer contained a curable part.

By this process, a desired A-M-C type copolymer was obtained.

The results are summarized in Tables 7 and 8.

Example 19

Synthesis of Copolymer (A-M-C Type) Containing PFPE Group and Curable Part (2)

A copolymer of A-M-C type was synthesized by the same procedure as in Example 18 except that the amount of the monomer to be used was changed and cation polymerization was carried out using PFPE4000VETFA as a polymerization initiator.

The amount and type of the monomers used and the like are shown in Table 3.

Example 20

Synthesis of a copolymer (A-M-B-N type) containing a PFPE group and a curable part (3)

In the indication of the type of copolymer, A represents a moiety having a PFPE group. And B represents a block containing a constituent unit having a curable part. And M represents a block containing a constituent unit not containing a curable part. N represents a terminal group having no curable part.

2.0 mL (PFPE4000 VETFA diluted with 0.1 mol / L in advance with HCFC-225) (corresponding to 0.2 mmol) as a cationic polymerization initiator containing PFPE in a dry nitrogen atmosphere, and HCFC-225 5.68 mL, and 1.0 mL of 1,4-dioxane. Further, 0.32 mL (0.5 M) of IBVE was added under dry nitrogen to make the total volume 9.0 mL, and the mixture was cooled to 0 캜. The mixture was stirred in an ice bath under nitrogen pressure using a magnetic stirrer, . On the other hand, discloses the polymerization of ethyl aluminum sesquichloride (Et ₁ _.5 AlCl ₁ _.5) and the reaction mixture rapidly under dry nitrogen in 1mL (0.2mmol) diluted in HCFC-225 in a polymerization solvent in advance which had a constant temperature in Chemistry 0 ℃ After 5 minutes, 0.12 mL (1.2 mmol) of AcVE diluted twice with HCFC-225 as a monomer containing a curable part was added. After 60 minutes, a methanol solution of 1% ammonia was added to stop the reaction.

By this process, a desired AMBA type copolymer was obtained.

The results are summarized in Tables 7 and 8.

Example 21 to 23

Synthesis of Copolymer (A-M-B-N Type) Containing PFPE Group and Curable Part (4)

A-M-B-N type copolymer was synthesized by the same procedure as in Example 20 except that the amount of the monomer to be used was changed and cation polymerization was carried out using PFPE4000 VETFA as a cationic polymerization initiator.

The amounts and types of the monomers used, and the like are shown in Table 4.

Example 24

Synthesis of a copolymer (A-M-B-N type) containing a PFPE group and a curable part (5)

In the indication of the type of copolymer, A represents a moiety having a PFPE group. And B represents a block including a constituent unit having a curable part. And M represents a block containing a constituent unit not containing a curable part. And N represents a terminal group having no curable part.

2.0 mL (previously diluted with 0.1 mol / L of HCFC-225) of PFPE4000VETFA (corresponding to 0.2 mmol) as a cationic polymerization initiator containing PFPE, 5.8 mL of HCFC-225 as a polymerization solvent And 1.0 mL of 1,4-dioxane. (1) 0.16 mL (1.2 mmol) of isobutyl vinyl ether [IBVE, CH ₂ = CH-O-CH ₂ CH (CH ₃ ) ₂ ] as a monomer having no curable component and (2) , 0.12 mL (1 mmol) of AcVE diluted with HCFC-225 in two times was added under dry nitrogen to make 9.0 mL as a whole, and the mixture was cooled to 0 占 폚. Then, under nitrogen pressure and using an magnetic stirrer Followed by stirring and cooling at 0 ° C. To this, and initiating polymerization of ethyl aluminum sesquichloride (Et ₁ _.5 AlCl ₁ _.5) and the reaction mixture rapidly under dry nitrogen in 1mL (0.2mmol) which had been diluted into 0 ℃ HCFC-225 as the polymerization solvent in advance, After 60 minutes, a methanol solution of 1% ammonia was added to stop the reaction.

By this process, an A-M-B-N type copolymer containing a PFPE group and a curable part was obtained.

The results are summarized in Tables 7 and 8.

Example 25

Synthesis of Copolymer (A-M-B-N Type) Containing PFPE Group and Curable Part (6)

Here, A represents a moiety having a PFPE group. And B represents a block including a constituent unit having a curable part. And M represents a block containing a constituent unit not containing a curable part. And N represents a terminal group having no curable part.

(0.2 mmol) (previously diluted with 0.1 mol / L of HCFC-225) of PFPE4000VETFA as a cationic polymerization initiator containing PFPE group, 5.68 mL of HCFC-225 as a polymerization solvent, 1.0 mL of 1,4-dioxane was added. Further, 0.32 mL (1.5 mmol) of 5FVE as a monomer containing no curable part was added under dry nitrogen to make 9.0 mL as a whole, and the mixture was cooled to 0 占 폚. Then, under nitrogen pressure and using an magnetic stirrer Followed by stirring and cooling at 0 ° C. To this, 1 mL (0.2 mmol) of ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) diluted with a polymerization solvent HCFC-225 beforehand was rapidly added under dry nitrogen to initiate polymerization, and after 5 minutes, 0.12 mL (1 mmol) of AcVE diluted with HCFC-225 (0.24 mL as HCFC-225 solution) was added as a monomer containing a curable part, and after 60 minutes, a methanol solution of 1% ammonia was added to stop the reaction .

By this process, an A-M-B-N type block copolymer containing a PFPE group and a curable part was obtained.

The results are summarized in Tables 7 and 8.

Example 26

Synthesis of a copolymer (A-M-B-N type) containing a PFPE group and a curable part (7)

A-M-B-N type copolymer was synthesized by the same procedure as in Example 25 except that the amount of the monomer to be used was changed and cation polymerization was carried out using PFPE4000VETFA as a cationic polymerization initiator.

The amount and kinds of the monomers used, and the like are shown in Table 5.

Example 27

Synthesis of a copolymer (A-M-B-N type) containing a PFPE group and a curable part (8)

2.0 mL (previously diluted with 0.1 mol / L of HCFC-225) (corresponding to 0.2 mmol) of PFPE4000VETFA as a cationic polymerization initiator containing PFPE group, 5.8 mL of HCFC-225 as a polymerization solvent, 1.0 mL of 1,4-dioxane was added. Further, 0.12 mL (1 mmol) of AcVE diluted with HCFC-225 twice as a monomer containing (1) 0.32 mL (1.5 mmol) of 5FVE as a monomer having no curing component and 2) a curable component 0.24 mL) was added under dry nitrogen to make 9.0 mL of the whole, and the mixture was cooled to 0 占 폚, stirred under a nitrogen pressure and in an ice bath using a magnetic stirrer, and then cooled at 0 占 폚. To this, and initiating polymerization of ethyl aluminum sesquichloride (Et ₁ _.5 AlCl ₁ _.5) and the reaction mixture rapidly under dry nitrogen in 1mL (0.2mmol) which had been diluted into 0 ℃ HCFC-225 as the polymerization solvent in advance, After 60 minutes, a methanol solution of 1% ammonia was added to stop the reaction.

By this process, an A-M / B-N type block copolymer containing a PFPE group and a curable part was obtained.

The results are summarized in Tables 7 and 8.

Example 32

Synthesis of Copolymers Containing Curable Parts at Both Termini of PFPE Group

(Equivalent to 0.2 mmol) (previously diluted with HCFC-225 at 0.1 mol / L) as a PFPE group-containing cationic polymerization initiator as a polymerization initiator in a dry nitrogen atmosphere, 5.7 mL of HCFC-225 and 1.0 mL of 1,4-dioxane were added. (1) 0.12 mL (1.6 mmol) of MOVE as a monomer containing no curing component and (2) 0.12 mL (1 mmol) of McVE diluted twice with HCFC-225 as a monomer containing a curable component were added under dry nitrogen , And the whole was adjusted to 9.0 mL. The mixture was cooled to 0 占 폚, stirred under nitrogen pressure and in an ice bath using a magnetic stirrer, and then cooled at 0 占 폚.

On the other hand, diluted with HCFC-225 in a polymerization solvent in advance, and the ethyl aluminum sesquichloride (Et ₁ _.5 AlCl ₁ _.5) of the screen which had a constant temperature to 0 ℃, 1mL (0.2mmol) was added quickly in dry nitrogen Polymerization was initiated, and after 60 minutes, a methanol solution of 1% ammonia was added to stop the reaction.

The reaction solution was transferred into methanol, and the resulting precipitate was reprecipitated with chloroform-methanol, and dried under reduced pressure to obtain the desired product.

¹ H-NMR (CDCl ₃ ):? 0.75-0.95 (m), 1.00-2.10 (m), 2.15-2.40 (m), 3.30 (bs), 3.40-4.00 (m), 4.15-4.40 4.60-4.70 (m), 5.25-5.45 (m), 5.45-5.80 (m), 6.00-6.15 (m).

Methoxy group derived from MOVE is observed at 3.30 ppm. From the point that the olefin protons derived from methacrylate were observed at 5.45-5.80 ppm and 6.00-6.15 ppm, and the olefin protons derived from vinyl ether were not observed at 4 ppm and 6.5 ppm, the vinyl ether units were cationically polymerized and cured The methacrylate unit as a site suggests that it remains unreacted.

From the above, it was confirmed that a polymer having a desired structure was obtained.

Synthetic example 7b

Synthesis of Vinyl Ether Containing PFPE

1 g (0.13 mmol) of an alcohol (number average molecular weight: 7470) containing a perfluoropolyether group and represented by the following chemical formula: PFPE-CH ₂ OH, 1 g (2.9 mmol) of tetrabutylammonium hydrogen sulfate, , 2 mL of a 40% aqueous sodium hydroxide solution and 10 mL of m-hexafluoroxylene, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To the mixture was added 2 mL of 2-chloroethyl vinyl ether, a dimox cooler was provided, and the mixture was stirred at 85 캜 for 72 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled off with a solvent in an evaporator until it was almost completely dried. The remaining reactants were dissolved in FC-72. This solution was extracted three times with dichloromethane to remove the coagulant (the end point was checked by TLC using an extraction solution.) The developing solvent HCFC225 was detected by spraying with a potassium permanganate solution and heating the spot at the origin .). The solvent was distilled off under reduced pressure to obtain the desired product.

Quantity 0.94g (93%)

The structure of the target substance was confirmed by NMR spectrum.

^{_{1 H-NMR (CDCl 3 -C}} 6 F 6): δ 3.86-3.96 (5H, m), 4.08-4.13 (3H, m), 6.38-6.42 (1H, m).

^{_{19 F-NMR (CDCl 3 -C}} 6 F 6): δ-82.90 - -83.10 (m), -83.35 - -83.50 (m), -84.40 (bs), -84.65 (bs), -84.90 (bs) -85.15 (bs), -85.60 - -85.80 (m), -87.50- -87.65 (m), -89.00 (s), -89.90 to -90.02 125.68 (t, J = 13.8 Hz), -126.50 to -126.80 (m), -128.00 (bs), -130.40 (s), -130.60 (bs), -131.10 (s), -131.60 (s).

The peak of the CF ₂ group of -128.74 (t) ppm at the? -Position of the starting alcohol disappeared and the peak of -125.68 (t) ppm was detected, thereby confirming the formation of the ether group.

Synthetic example 8

Synthesis of PFPE-containing vinyl ether trifluoroacetic acid adduct (PFPE group-containing cationic polymerization initiator)

Under a dry nitrogen atmosphere, an HCFC-225 solution (1 mL) in which an equal amount of trifluoroacetic acid was dissolved in HCFC-225 solution (5 mL) of vinyl ether (0.9 g) containing PFPE obtained in Synthesis Example 7b was stirred at 0 ° C Lt; / RTI > The mixture was stirred at this temperature for 10 minutes to synthesize a cationic polymerization initiator containing PFPE group.

The formation of the desired product was confirmed by disappearance of vinyl H (6.4 ppm) and methine H (5.9 ppm) of acetic acid adduct in 1 H-NMR.

This compound was used in the polymerization reaction without purification.

Comparative Example One

Synthesis of Copolymer Containing PFPE (A-M-N Type) (1)

2.0 mL (corresponding to 0.2 mmol) of PFPE4000 VETFA (previously diluted with HCFC-225 at 0.1 mol / L) as a cationic polymerization initiator containing PFPE group (sometimes abbreviated as Rf initiator) , 5.68 mL of HCFC-225 (AK225, Asahi Glass) as a polymerization solvent and 1.0 mL of 1,4-dioxane as a base were added. Further, 0.32 mL (1.5 mmol) of 5FVE as a monomer containing no curable part was added under dry nitrogen to make 9.0 mL as a whole, and the mixture was cooled to 0 占 폚. Then, using nitrogen stoichiometry and a magnetic stirrer Followed by stirring and cooling at 0 ° C. To this, 1 mL (0.2 mmol) of ethylaluminum sesquichloride (Et _1.5 AlCl _1.5 ) diluted with a polymerization solvent HCFC-225 as a polymerization catalyst was added at a rapid rate under dry nitrogen to initiate polymerization, and 60 minutes Thereafter, a methanol solution of 1% ammonia was added to terminate the reaction.

By this process, an A-M-N type block copolymer containing a PFPE group was obtained.

Purification of the resulting polymer was carried out in the same manner as in Example 1. By NMR measurement, it was confirmed that there was no residue of open cell and no peak of C = C bond, and it was confirmed that the resulting polymer did not contain a curable part.

The conversion of the resulting polymer was calculated in the same manner as in Example 1, and GPC measurement was carried out.

The results are summarized in Table 7.

Comparative Example 2 to 8

Synthesis of Copolymer Containing PFPE Group (A-M-N Type) (2 to 8)

Except that the amount and kind of the monomers to be used were changed and cationic polymerization was carried out using PFPE4000VETFA as a cationic polymerization initiator to synthesize an A-M-N type copolymer.

The amount and kinds of the monomers used, and the like are shown in Table 6.

The conversion of the resulting polymer was calculated in the same manner as in Example 1, and GPC measurement was carried out. The results are summarized in Table 7.

In the column " Structure " in Table 7, the structures of the respective copolymers are represented by symbols. Here, the number of the subscripts attached to the structural unit derived from the monomer represents the number of repeats. -b- represents that the constituent unit forms a block, and -r- represents that the constituent unit is bonded at random. The same notation may be used in addition to Table 7 in this specification.

Test Example One

(1) A commercially available hard coating beam set 575CB (manufactured by Arakawa Chemical Industries, Ltd.) was dissolved in MIBK, and a solution obtained in Examples 1, 10, 11, 14, 20, 24, 25 and 27 , And PFPE were added to the hard coating resin solids so as to be 1% in terms of solids concentration to obtain a total solid content concentration of about 0.4% to obtain a hard coating agent containing PFPE.

The above PFPE-containing hard coating agent was dip-coated (pulling rate: 4.0 mm / sec) on a commercially available polycarbonate substrate (50 mm x 50 mm, manufactured by Mitsubishi Heavy Industries, Ltd.) and dried at 70 캜 for 5 minutes. To obtain a cured coating. The ultraviolet ray irradiation was performed using a belt conveyor type ultraviolet ray irradiation apparatus, and the dose was 600 mJ / cm ² .

The appearance of the cured film obtained was visually evaluated, and the logarithmic contact angle and the contact angle of the major HD (normal hexadecane) were measured. The results are shown in Table 9.

The oil-based ink scrubbing (easy cleaning of oil ink) was tested as follows. First, oil-based ink was applied to the surface of the cured coating with a oil-based ink pen (Sakura pen touch), and the appearance was visually evaluated. Subsequently, after drying, it was wiped with Kimwipe S-200, and the appearance was visually evaluated. The results are shown in Table 9.

(2) A cured film was obtained in the same manner as in the above (1) except that a commercially available perfluoropolyether derivative, DEMNUM S-20 (number average molecular weight 2600, Daikin Kogyo Co.) was used as the PFPE-containing polymer.

However, since the cured film itself was opaque and the oil-like liquid was separated on the surface, only the appearance was observed as a test.

(3) A cured film was obtained in the same manner as in Comparative Example 1 except that S-65 (average molecular weight: 4,500, Daikin Kogyo Co.) was used instead of S-20. Since the cured film itself was opaque and the oil-like liquid was separated on the surface, only the appearance was observed as a test.

(4) A cured film was obtained in the same manner as in (1) except that the copolymer obtained in Comparative Examples 1 to 8 was used as the copolymer containing PFPE. The same evaluation as in (1) above was carried out. The results are shown in Table 9.

[Exterior]

○: Transparent

?: Translucent

×: cloudiness

[Oil-based ink - crater ring]

&Amp; cir &: Ink turned around, almost not left

○: Ink turned around and did not line up

△: The ink is out, but the line remains.

X: The ink was not rolled up, and the line could be drawn

[Oily ink-scrubbing]

◎: The ink could be wiped very lightly, but not at all

○: The ink could be wiped off, but not on the surface.

△: The ink could not be wiped off and remained on the surface a little

X: The ink could not be wiped off and remained on the surface.

Example 33

PFPE4000VETFA (0.2 mmol) was used as a cationic polymerization initiator containing PFPE (MW: 4000) group, 5.82 mL of HCFC-225 as a polymerization solvent, and 1,4-dioxane 1.0 mL. Further, 3- (triethoxysilyl) propyl vinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 占 폚. To the reaction solution, with stirring, and ethyl aluminum sesquichloride: was added to initiate polymerization HCFC-225 solution of _{(Et 1 .5 AlCl 1 .5 0.2mmol} ). After stirring at this temperature for 5 minutes, anhydrous ethanol: HCFC-225 (1: 1) was added to terminate the polymerization reaction. The reaction solution was diluted with HFE7200 and perfluorohexane, and separated into two phases by Freon solution-ethanol by standing, and the ethanol phase was removed. The remaining Freon solution was dried under reduced pressure to obtain a polymer having the above structure.

[Wherein m and n each represent the number of repeating units]

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.10-0.45 (m), 0.50-1.05 (m), 1.05-1.80 (m), 2.90-3.65 (m), 3.65-3.90 .

MALDI-TOF-MS (KRATOS AXIMA-CFR type); Positive mode, no matrix.

A graph is shown in Fig.

From this data, n = 22 and m = 3 were indicated.

Example 34

[Wherein m and n each represent the number of repeating units]

(0.2 mmol) of PFPE vinyl ether trifluoroacetic acid adduct (PFPE (MW: 4000) group-containing cationic polymerization initiator), 5.82 mL of HCFC-225 as a polymerization solvent, Was added 1.0 mL of 1,4-dioxane. Further, 3- (trimethoxysilyl) propyl vinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 占 폚. To this reaction solution, under stirring, an HCFC-225 solution of ethyl aluminum sesquichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) was added to initiate polymerization. After stirring at this temperature for 5 minutes, anhydrous methanol: HCFC-225 (1: 1) was added to terminate the polymerization reaction. The reaction solution was diluted with HFE7200 and perfluorohexane, and separated into two phases of Freon solution-methanol by standing to remove the methanol phase. The remaining Freon solution was dried under reduced pressure to obtain a polymer (Polym1) having the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.10-0.45 (m), 1.05-1.80 (m), 2.90-3.65 (m), 3.65-3.90 (m).

Example 35

[Wherein m and n each represent the number of repeating units]

Ethyl 1- (1-propenoxy) -2- (2-triethoxysilylethoxy) ethane was synthesized in accordance with the existing literature (Crivello, JV et al., Chem. ).

(0.375 mmol) of PFPE vinyl ether trifluoroacetic acid adduct (0.375 mmol) as a cationic polymerization initiator containing PFPE (MW: 4000) group, 5.7 mL of HCFC-225 as a polymerization solvent, Was added 1.0 mL of 1,4-dioxane. From 0 ℃, here the 1- (1-propenyl phenoxy) -2- (2-ethoxy-tree to silyl ethoxy) ethane _{[MW: 292, CH 3 CH} = CHO (CH 2) 2 O (CH 2) 2 Si (OCH ₂ CH ₃ ) ₃ ] (0.3 mL, 1 mmol). The reaction vessel was immersed in a low-temperature bath at -30 캜 and stirred for 24 hours. While maintaining the temperature, 2 mL of anhydrous ethanol: HCFC-225 (1: 1) solution cooled to -30 占 폚 was added and the reaction was stopped. The reaction solution was diluted with HFE7200 and perfluorohexane, and separated into two phases of Freon solution-ethanol by standing, and the ethanol phase was removed. The remaining Freon solution was washed with absolute ethanol and then dried under reduced pressure to obtain a polymer having the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O):? 0.40-1.60 (m), 2.60-3.70 (m), 3.70-4.10 (m).

Example 36

[Wherein m and n each represent the number of repeating units]

(0.375 mmol) of PFPE vinyl ether trifluoroacetic acid adduct (0.375 mmol) as a cationic polymerization initiator containing PFPE (MW: 4000) group, 5.7 mL of HCFC-225 as a polymerization solvent, Was added 1.0 mL of 1,4-dioxane. From 0 ℃, where 3- (triethoxysilyl) propylamino the carboxylic acid 2- (vinyloxy) ethyl ester _{[CH 2 = CHO (CH 2} ) 2 OCONH (CH 2) 3 Si (OCH 3) 3] (1 mmol) were added to the solution, and the mixture was stirred at this temperature for 24 hours. While maintaining the temperature, 2 mL of anhydrous methanol: HCFC-225 (1: 1) solution was added, and the reaction was stopped. The reaction solution was diluted with HFE7200 and perfluorohexane, and separated into two phases of Freon solution-methanol by standing, and the methanol phase was removed. The remaining Freon solution was washed with anhydrous methanol and then dried under reduced pressure to obtain a polymer having the above structure.

¹ H-NMR (C ₆ F ₆ -D ₂ O): δ 0.60-0.80 (m), 0.80-2.20 (m), 3.00-3.20 (m), 3.20-4.05 ).

Example 37a and 37b

[Wherein m and n each represent the number of repeating units]

Example 37a Structure: PFPE4000-McVE ₉ -OMe

Methacrylic acid 2- (vinyloxy) ethanol ester was synthesized by the existing literature (Sugihara et al., Macromolecules, 2007, Vol. 40, p. 3394).

(0.2 mmol) of PFPE vinyl ether trifluoroacetic acid adduct (PFPE (MW: 4000) group-containing cationic polymerization initiator), 5.82 mL of HCFC-225 as a polymerization solvent, Was added 1.0 mL of 1,4-dioxane. Further, an HCFC-225 solution (0.6 mL) of methacrylic acid 2- (vinyloxy) ethanol ester CH ₂ = CHOCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (302 mg, ₂ mmol) And cooled. To this reaction solution, under stirring, an HCFC-225 solution of ethyl aluminum sesquichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) was added to initiate polymerization. After stirring at this temperature for 60 minutes, a methanol solution of 1% ammonia was added to terminate the polymerization reaction. The solvent was distilled off under reduced pressure to obtain a polymer having the above structure.

^{_{1 H-NMR (C 6 F}} 6 -D 2 O): δ 1.00 - 1.10 (m), 1.40-2.00 (m), 2.00 - 2.50 (m), 3.10 (bs), 3.15-3.95 (m), 4.00 - 4.20 (m), 5.40 (bs), 5.90 (bs).

From the integral value of the methyl group and vinyl H derived from the initiator detected at 1.00-1.10, m = 9 was estimated.

Example 37b Structure: PFPE4000-McVE ₂₀ -OMe

An HCFC-225 solution of PFPE vinyl ether trifluoroacetic acid adduct (0.2 mmol) and McVE (CH ₂ ═CHOCH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ : 602 mg, 4 mmol) was added in the same manner as in Example 37a, HCFC-225 from, ethylaluminum sesquichloride: was polymerized using _{(Et 1 .5 AlCl 1 .5 0.2mmol} ) ( reaction temperature 0 ℃; reaction time 60 minutes). After removal of the solvent by distillation, it was confirmed by ¹ H-NMR measurement that a polymer having the number of m in the above formula was obtained.

Synthetic example 9

Synthesis of PFPE-Z-diol-1, omega -bis (vinyloxyethoxy) ether

CH ₂ = CH-OC ₂ H ₅ -OCH ₂ -CF ₂ - (OCF ₂ ) _m - (OCF ₂ CF ₂ ) _n -OCF ₂ -CH ₂ OC ₂ H ₅ O-CH = CH ₂

[Wherein m and n each represent the number of repeating units]

In a 20 mL eggplant-shaped flask,

1 g (0.25 mmol) of PFPE-Z-diol (Pomphlaine Z-dol (trade name), number average molecular weight 4000, manufactured by Solvay), 850 mg (2.5 mmol) of tetrabutylammonium hydrogen sulfate, 2 mL of a 40% aqueous sodium hydroxide solution, 5 mL of fluoroxylene was added thereto, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To the mixture was added 2 mL of 2-chloroethyl vinyl ether, and a dimox cooler was attached to an eggplant type flask. The mixture was stirred at 70 캜 for 72 hours under a nitrogen atmosphere. After cooling, the reaction solution was distilled off with a solvent in an evaporator until it was almost completely dried. The remaining reactants were dissolved in a fluorine-based inert liquid (Fluorinert FC-72 (trade name), Sumitomo 3M Co.). This solution was extracted three times with acetone and then dichloromethane to remove the coagulated matter. Here, the removal of the coalescence was judged by checking the extract with TLC (developing solvent: HCFC-225, detection method: spraying and heating of potassium permanganate solution, judgment standard: spot disappearance at the origin). The solvent was distilled off under reduced pressure to obtain the desired product.

Hereinafter, this compound is abbreviated as PFPE-Z-diol bisvinyl ether. Also, the amount is 650 mg (63%).

The structure of the target substance was confirmed by NMR spectrum.

¹ H-NMR (C ₆ F ₆ -D ₂ O):? 3.40-3.57 (5H, m), 3.59-3.74 (3H, m), 5.88-5.96 (1H, m).

^{_{19 F-NMR (C 6 F}} 6 -D 2 O): δ -51.5 (bs), -53.1 (bs), -54.8 (bs), -77.2 (bs), -79.2 (bs), -88.5 (bs ), -90.1 (bs).

The peaks of the CF ₂ group (-80.4 ppm and -82.4 ppm) at the β-position of the starting alcohol were lost, and peaks at -77.2 ppm and -79.2 ppm were detected, thereby confirming formation of an ether group.

Synthetic example 10

Synthesis of cationic polymerization initiator containing PFPE-Z group

_{CH 3 CH (OCOCF 3) -OCH} 2 CH 2 -OCH 2 CF 2 - (OCF 2) m - (OCF 2 CF 2) n -OCF 2 CH 2 -OCH 2 CH 2 -OCH (OCOCF 3) CH ₃

[Wherein m and n each represent the number of repeating units]

In the same manner as in Synthesis Example 2, a polymerization initiator having the above structure was synthesized from TFA and PFPE-Z-diol bisvinyl ether.

^The structure was confirmed by disappearance of vinyl H near 6 ppm by ¹ H-NMR and appearance of methine H derived from acetal ester near 5.5 ppm.

Synthetic example 11

Synthesis of vinyl ether having a silane coupling group as a curing component (3)

Allyl vinyl ether (9.0 g, 107 mmol) was slowly added dropwise at room temperature to a dry toluene solution (220 mL) of triethoxysilane (20.99 g, 128 mmol) and hexachloroplatinum (IV) acid · hexahydrate (55 mg, 0.11 mmol) Respectively. After stirring at room temperature for 18 hours, the reaction solution was filtered through celite, and the obtained filtrate was concentrated under reduced pressure. The remaining reaction product was distilled under reduced pressure (bp 70 ° C, 1 mmHg) to obtain 19.6 g (yield: 74%) of the desired product.

^{_{1 H-NMR (CDCl 3)}} : δ 0.60-0.68 (2H, m), 1.18 (9H, t, J = 6.8Hz), 1.68-1.78 (2H, m), 3.35 (2H, t, J = 6.4Hz D, J = 14.2, 6.9 Hz), 3.78 (6H, q, J = 6.8 Hz), 3.93 (1H, d, J = 6.9 Hz) ).

Synthetic example 12

Synthesis of vinyl ether having a silane coupling group as a curable part (4)

In the same manner as in Synthesis Example 11, vinyl ether 4 having a silane coupling group was synthesized using trimethoxysilane (bp 56 ° C, 100 Pa).

^{_{1 H-NMR (CDCl 3)}} : δ 0.48-0.60 (2H, m), 1.55-1.75 (2H, m), 3.31 (9H, s), 3.30-3.55 (2H, m), 3.78-3.85 (1H, m), 3.90-4.10 (IH, m), 6.23-6.35 (IH, m).

Example 38

[Wherein m, n, p and q each represent the number of repeating units]

(0.2 mmol) of the PFPE (Pompholin Z) group-containing cationic polymerization initiator (0.2 mmol) prepared in Synthesis Example 10 as a PFPE group-containing cationic polymerization initiator, 5.82 mL of HCFC-225 as a polymerization solvent And 1.0 mL of 1,4-dioxane as an addition base. Further, 3- (triethoxysilyl) propyl vinyl ether (4 mmol) was added to make 9.0 mL of the whole, and the mixture was cooled to 0 占 폚. To this reaction solution, under stirring, an HCFC-225 solution of ethyl aluminum sesquichloride (Et _1.5 AlCl _1.5 : 0.2 mmol) was added to initiate polymerization. After stirring at this temperature for 5 minutes, anhydrous ethanol: HCFC-225 (1: 1) was added to terminate the polymerization reaction. The reaction solution was diluted with HFE7200 and perfluorohexane, and separated into two phases of Freon solution-ethanol by standing, and the ethanol phase was removed. The remaining Freon solution was dried under reduced pressure to obtain a polymer having the above structure.

^{Since 1} H-NMR showed no vinyl H and acetal ester methine H, it was confirmed that the target product was obtained.

Synthetic example 13

Synthesis of vinyl ether having a silane coupling group as a curing component (5)

A vinyl ether 5 having a trichlorosilyl group was synthesized by using trichlorosilane in the same manner as in Synthesis Example 11 (bp 56 ° C, 100 Pa).

^{_{1 H-NMR (CDCl 3)}} : δ 0.99-1.08 (2H, m), 1.80-1.98 (2H, m), 3.40-3.55 (2H, m), 3.80-3.85 (1H, m), 3.88-4.05 ( 1H, < / RTI > m), 6.25-6.30 (1H, m).

Example 39

[In the formula, m represents the number of repeats]

PFPE vinyl ether trifluoroacetic acid adduct (0.2 mmol) as a cationic polymerization initiator containing PFPE (MW: 4000) group, 5.82 mL of HCFC-225 as a polymerization solvent, and 1,4-di 1.0 ml of oxalic acid was added. Further, 3- (trichlorosilyl) propyl vinyl ether (4 mmol) was added to make 9.0 mL of the whole, followed by cooling to 0 占 폚. To the reaction solution, with stirring, and ethyl aluminum sesquichloride: was added to initiate polymerization HCFC-225 solution of _{(Et 1 .5 AlCl 1 .5 0.2mmol} ). After stirring at this temperature for 5 minutes, the reaction solution was cooled to 0 占 폚, dimethylamine: HCFC-225 (1: 1) was added, and further stirred at room temperature for 15 hours. The reaction solution was diluted with perfluorohexane and tetrahydrofuran (THF), separated into two phases of perfluorohexane solution-THF by standing, and the THF phase was removed. The remaining perfluorohexane solution was dried under reduced pressure to obtain a polymer (Polym2) having the above structure.

In the comparison of the ¹ H-NMR of the product with the intermediate of the reaction, the structure of the target product was confirmed by detecting a singlet at 2.9 ppm derived from N-CH ₃ in the product.

Test Example 2

As Example 40, the polymer (Polym1) obtained in Example 34 and the following two types of perfluoropolyether compounds (a, b) having the following structures were mixed at 50:20:30 to prepare a solution of HFE7200 , A glass substrate (chemical tempered glass manufactured by Corning Incorporated, gorilla (trade name) glass, thickness 0.7 mm) and dried to form a film.

a CF ₃ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₃ Average molecular weight 12500

b: CF ₃ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₃ average molecular weight 8000

[Wherein, p and q are each a repetition number]

Further, as Example 41, a Polym 1 coating film was formed on a glass substrate in the same manner as in Example 40.

As Comparative Examples 11 and 12, coatings of the compound a or the compound b were formed on a glass substrate in the same manner as in Example 40, respectively.

As Example 42, a coating film of the polymer (Polym 2) obtained in Example 39 was formed on a glass substrate in the same manner as in Example 40.

(3) kinematic friction coefficient (surface sliding property), and (4) number of times of abrasion durability of the compound coating film obtained after drying (Wear durability) was evaluated or measured.

The criteria for each item are as follows.

(1) Appearance

(Visual inspection) : The evaluation was made according to the following criteria.

○: No particle present on the coating surface after coating and drying

X: presence of particles at the coating surface after coating drying

(Degree of cloudiness) : haze value (%: measured by haze meter)

(2) Feeling of feeling with the fingers (surface slip property ) : Sensory evaluation The panel list was touched with the fingers of the film surface, and the feeling of use was evaluated according to the following criteria.

1: very good

2: Good

3: Usually

4: Bad

(3) Coefficient of dynamic friction (surface slip property )

The coefficient of dynamic friction (-) was measured in accordance with ASTM D1894 using a steel gauge as a friction member using a surface tester ("TREVORER 14FW type" manufactured by Shinto Kagaku Kabushiki Kaisha).

(4) Abrasion Durability (Wear Durability)

The steel wool (number # 0000, size 10 mm x 10 mm x 5 mm) was brought into contact with the membrane surface and was reciprocated at a speed of 140 mm / sec under a load of 1000 gf.

After 500 reciprocations, the static contact angle of water was measured (the logarithmic contact angle was measured with a liquid amount of 1 mu L in water using " DropMaster ", manufactured by Kyowa Chemical Co., Ltd.). The abrasion durability was defined as the number of times of friction at which the contact angle became 100 DEG C or less.

The results obtained in Examples 40 to 42 and Comparative Examples 11 and 12 are incorporated in the following table.

Example 43 to 54

Synthesis of Copolymer Containing PFPE Group and Curable Part (A-B-N Type) (3)

Example 43

(HCFC-225; 4.0 mmol) of a monomer McVEE solution (corresponding to 0.2 mmol of HCFC-225) and a curing component as a PFPE4000 VETFA solution as a PFPE group-containing cationic polymerization initiator was obtained in the same manner as in Example 1, -Dioxane (5.26 mL-1.0 mL) was polymerized (8 min) using 1 mL of an ethylaluminum sesquichloride solution (HCFC-225; Et _1.5 AlCl _1.5 : 0.2 mmol) at 0 ° C. under dry nitrogen. After the post-treatment, the structure was confirmed by NMR and GPC.

Mn x 10 ^-3 = 5.6 Mw / Mn = 1.21

^{_{1 H-NMR (CDCl 3)}} : δ 1.05-1.20 (m), 1.40-2.00 (m), 1.95 (bs), 3.30 (bs), 3.35-3.80 (m), 3.80-4.0 (m), 4.20- 4.40 (m), 5.50-5.60 (m), 6.05-6.15 (m).

From the proton integral values of the terminal OCH ₃ groups observed at 3.3 ppm and the olefin protons observed at 5.50-5.60 ppm and 6.05-6.15 ppm, the block ratio of the terminal PFPE group and the curable part (m in the above formula) was estimated to be 20.

In the same procedure as in Example 43, the compounds of Examples 44 to 54 were synthesized under the conditions and materials listed in Table 11, and the number of m in the formulas was also estimated.

Various physical properties were measured in the same manner as in Example 1 with respect to some of them. The results are summarized in Tables 12 and 13.

*: HFE7200 was used instead of AK225 as a polymerization solvent.

Example 55

(HCFC-225; 2.0 mmol) of a solution of the PFCE group-containing cationic polymerization initiator (polymerization initiator 5c) (corresponding to 0.2 mmol of HCFC-225) and the monomer McVEE solution 1,4-dioxane (5.63mL-1.0mL) to, quinone chloride solution at 0 ℃ ethylaluminum process under dry nitrogen 1mL solution;: polymerization using _{(HCFC-225 Et 1 .5 AlCl} 1 .5 0.2mmol) (30 minutes). After the post-treatment, the structure was confirmed by NMR.

¹ H-NMR (CDCl ₃ ): δ 1.10 (bs), 1.40-2.00 (m), 1.95 (bs), 3.30 (bs), 3.35-3.80 (m), 3.80-4.0 m), 5.50-5.60 (m), 6.05-6.15 (m).

From the proton integral values of the terminal CH ₃ groups observed at 1.1 ppm and the terminal OCH ₃ groups observed at 3.3 ppm and the olefin protons observed at 5.50-5.60 ppm and 6.05-6.15 ppm, the block ratio of the terminal PFPE group and the curable part was 10 Respectively.

?: Transparent and uniformly soluble.

B: Turbidity was present but dissolved.

X: Not dissolved.

[Oil-based ink - crater ring]

◎: Ink turned around and almost remained.

○: The ink turned outward and did not line up.

?: The ink was turned around, but the line remained.

X: The ink was not rolled up, and the line could be drawn.

[Oily ink-scrubbing]

◎: The ink could be wiped very lightly, and it remained at all.

○: The ink could be wiped off, but not on the surface.

△: The ink could not be wiped off and remained on the surface a little.

X: The ink could not be wiped off and remained on the surface.

From the above results, the perfluoropolyether compound having no bonding unit with the substrate has high slidability and excellent feeling on use, but has a very low durability as a surface treated coating film. On the other hand, the compound of the present invention having a bonding group with a substrate has excellent durability, but there is an impression that the feeling of use is slightly lower than that of a perfluoropolyether compound. Compared with these, by combining a compound having a bonding group and a compound having no bonding group, it was found that a good surface-treated coating having both feeling and durability was obtained.

Further, it has been found that durability is further improved by using a silyl group as a silyl ether group as a bonding group with a substrate. This is believed to be due to the effect of the silazane group as a linking group.

[Industrial applicability]

The fluorine-containing copolymer of the present invention can suitably be used as a oil-repellent and / or water-repellent coating agent, having excellent oil and water repellency and high solubility in a general solvent (fluorine-free organic solvent).

Claims

Equation (1):

[Wherein,
R ^a1 represents a monovalent or divalent group containing a perfluoropolyether group.
X ^a represents -O-, phenylene, -N (-R ^E ) - (wherein R ^E represents an organic group), or carbazolylene.
R ^a2 represents a hydrogen atom or an alkyl group.
R ^a3 represents a hydrogen atom or an alkyl group.
Q represents a constituent unit containing a curable component or a constituent unit not containing a curable component in each occurrence independently of each other.
R ^c represents a group containing a perfluoropolyether group or an organic group which may contain a curable part or a hydrogen atom.
X ^c represents -O-, -S-, -NH- or a single bond.
k represents 1 or 2;
n1 represents a repetition number of 5 to 200;
only,
At least one of R ^a2 and R ^a3 is an alkyl group.
When R ^c is not an organic group containing a curable component, at least one Q is a structural unit containing a curable component.]
Is a fluorine-containing copolymer.

The method according to claim 1,
Q is a formula:

[Wherein,
Each occurrence of R ^b1 in each occurrence represents a hydrogen atom or an alkyl group.
R ^b2 represents, independently at each occurrence, an organic group which may contain a hydrogen atom or a curable part.
R ^b3 represents a hydrogen atom or an alkyl group.
X ^b represents -O-, phenylene, -N (-R ^E ) - (wherein R ^E represents an organic group), or carbazolylene.
only,
When R ^b2 is a hydrogen atom, X ^b is phenylene.]
Is a structural unit represented by the following formula (1).

3. The method according to claim 1 or 2,
The number average molecular weight of the perfluoropolyether group in the monovalent or divalent group containing a perfluoropolyether group represented by R ^a1 is 1000 or more.

3. The method according to claim 1 or 2,
The perfluoropolyether group in the group containing a perfluoropolyether group represented by R ^a1 is a group represented by the formula: - (C _p F _2p O) _n -
[Wherein,
p is, independently at each occurrence, an integer of 1 to 6 in each occurrence.
n represents the number of repeats.]
Wherein the fluorine-containing copolymer has a part represented by the following formula (1).

5. The method of claim 4,
R < ^a1 &
Formula: X ^ra - (C _p F _2p O) _na -Y ^ra -L ^a - (a1)
[Wherein,
X ^ra represents fluorine or R f -O- (R f represents a perfluoroalkyl group having 1 to 8 carbon atoms).
p represents, independently for each occurrence, an integer of 1 to 6;
and na represents the number of repeats from 1 to 1000.
Y ^ra represents a perfluoro alkylene chain having 1 to 6 carbon atoms.
L ^a represents a linker]
A fluorine-containing copolymer.

6. The method of claim 5,
The moiety represented by the formula (C _p F _2p O) _na in the formula (a1) is -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O-, -CF ₂ -O-, -CF ₂ -CF ₂ -O- and -CF (-CF ₃ ) -O-.

The method according to claim 6,
The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -CF ₂ -CF ₂ -O-,
Y ^ra is -CF ₂ -CF ₂ -, a fluorine-containing copolymer.

The method according to claim 6,
The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -CF ₂ -O- and -CF ₂ -O-,
Y ^ra is -CF ₂ -, a fluorine-containing copolymer.

The method according to claim 6,
The moiety represented by the formula: (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O-,
Y ^ra is -CF (-CF ₃ ) -, a fluorine-containing copolymer.

The method according to claim 6,
The moiety represented by the formula: (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O- and -CF ₂ -O-,
Y ^ra is -CF (-CF ₃ ) -, a fluorine-containing copolymer.

6. The method of claim 5,
L ^a is -CH ₂ -O-CH ₂ -CH ₂ -.

6. The method of claim 5,
L is ^a, -CH ₂ - is a fluorine-containing copolymer.

5. The method of claim 4,
R < ^a1 &
^???????? - L ^{a '} -Y ^ra' -O- (C _p F _2p O) _na -Y ^ra -L ^a - (a2)
[Wherein,
L ^{a '} and L ^a independently represent a linker.
Y ^{ra '} and Y ^ra each independently represent a perfluoroalkylene chain having 1 to 6 carbon atoms.
p represents, independently for each occurrence, an integer of 1 to 6;
and na represents the number of repeats from 1 to 1000.]
Is a divalent group represented by the following formula

14. The method of claim 13,
The moiety represented by the formula (C _p F _2p O) _na in the formula (a2) is independently selected from -CF ₂ -CF ₂ -CF ₂ -O-, -CF (-CF ₃ ) -CF ₂ -O -, -CF ₂ -O-, -CF ₂ -CF ₂ -O- and -CF (-CF ₃ ) -O-.

14. The method of claim 13,
Y ^{ra '} is -CF ₂ -CF ₂ -
The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -CF ₂ -CF ₂ -O-,
Y ^ra is -CF ₂ -CF ₂ -, a fluorine-containing copolymer.

14. The method of claim 13,
Y ^{ra '} is -CF ₂ -
The moiety represented by the formula: (C _p F _2p O) _na includes -CF ₂ -CF ₂ -O- and -CF ₂ -O-,
Y ^ra is -CF ₂ -, a fluorine-containing copolymer.

14. The method of claim 13,
Y ^{ra '} is -CF (-CF ₃ ) -,
The moiety represented by the formula: (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O-,
Y ^ra is -CF (-CF ₃ ) -, a fluorine-containing copolymer.

14. The method of claim 13,
Y ^{ra '} is -CF (-CF ₃ ) -,
The moiety represented by the formula: (C _p F _2p O) _na includes -CF (-CF ₃ ) -CF ₂ -O- and -CF ₂ -O-,
Y ^ra is -CF (-CF ₃ ) -, a fluorine-containing copolymer.

5. The method of claim 4,
The perfluoropolyether group in the group containing a perfluoropolyether group represented by R < ^a1 &^gt;
^{Formula: -L a '-Y ra' -} (OC p 'F 2p') na '-O-Rf-O- (C p F 2p O) na -Y ra -L a - (a2')
[Wherein,
L ^{a '} and L ^a independently represent a linker.
Y ^{ra '} and Y ^ra each independently represent a perfluoroalkylene chain having 1 to 6 carbon atoms.
p 'and p each independently represent an integer of 1 to 6 in each occurrence.
na ' and na each independently represent a repeating number of 1 to 1000.
And Rf represents a perfluoroalkylene chain.
Is a divalent group represented by the following formula

20. The method of claim 19,
Y ^{ra '} is -CF (-CF ₃ ) -,
The moiety represented by the formula: (OC _{p '} F _2p' ) _{na '} includes -O-CF ₂ -CF (-CF ₃ ) -,
Rf is a perfluoroalkylene chain having 1 to 8 carbon atoms,
The moiety represented by the formula: (C _p F _2p O) _na is -CF (-CF ₃ ) -CF ₂ -O-,
Y ^ra is -CF (-CF ₃ ) -, a fluorine-containing copolymer.

14. The method of claim 13,
L ^{a '} is -CH ₂ -CH ₂ -O-CH ₂ -, and also
L ^a is -CH ₂ -O-CH ₂ -CH ₂ -.

14. The method of claim 13,
L ^{a '} is -CH ₂ -, and
L is ^a, -CH ₂ - is a fluorine-containing copolymer.

3. The method according to claim 1 or 2,
R ^c is not an organic group containing a curable part,
And at least one Q is a structural unit containing a curable part.

24. The method of claim 23,
The curing component in Q is a (meth) acryloyl group or a silane coupling group.

24. The method of claim 23,
The constituent unit containing the curable part is a group bonded to X ^b via a curable addition linker,
Wherein the linker is independently - (CHR ^y ) _n -O- or - (CHR ^y ) _n -O- (CHR ^y ) _n -O- And R ^y represents, in each occurrence, each independently hydrogen or a methyl group.

24. The method of claim 23,
And R ^c is a methyl group.

3. The method according to claim 1 or 2,
And R < ^c > is an organic group containing a curable part.

28. The method of claim 27,
And R ^c is a group containing a silane coupling group.

The oil repellent and / or water repellent coating agent containing the fluorine-containing copolymer according to claim 1 or 2.

30. The method of claim 29,
Equation (2):
^{_{R r1 -O- (C r F 2r}} O) nd -R r2
[Wherein,
r is, independently for each occurrence, an integer of 1 to 6;
nd represents the number of repetitions.
And R ^r1 and R ^r2 each independently represent a perfluoroalkyl group having 1 to 16 carbon atoms.
And / or a water-repellent coating agent.

An article containing a coating formed from the oil repellent and / or water repellent coating agent according to claim 29.

delete

expression:

[Wherein,
PFPE _{is, -CF (-CF 3) - (} O-CF 2 -CF (-CF 3)) n -O-CF 2 -Rf-CF 2 -O- (CF (-CF 3) -CF 2 -O -) _{n '} -CF (CF ₃ ) - (Rf represents a perfluoroalkylene group, and n and n' each represent a repetition number).
Y ^a represents an acyloxy group or a halogen atom.
&Lt; / RTI >
_{Formula: CH 2 = CH-OC 2} H 4 -O-CH 2 -PFPE-CH 2 -OC 2 H 4 -O-CH = CH 2 ( Expression of the symbols represents the same meaning as defined above)
&Lt; / RTI >
Y ^a -H (wherein the symbols have the same meanings as defined above)
&Lt; / RTI > with a compound represented by formula < RTI ID = 0.0 >

expression:

[Wherein,
PFPE represents -CF ₂ CF ₂ -O- (CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repetition number).
Y ^a represents an acyloxy group or a halogen atom.
&Lt; / RTI >
_{Formula: CH 2 = CH-OC 2} H 4 -O-CH 2 -PFPE-CH 2 -OC 2 H 4 -O-CH = CH 2 ( Expression of the symbols represents the same meaning as defined above)
&Lt; / RTI >
Y ^a -H (wherein the symbols have the same meanings as defined above)
&Lt; / RTI > with a compound represented by formula < RTI ID = 0.0 >

expression:

[Wherein,
PFPE represents -CF ₂ CF ₂ -O- (CF ₂ -CF ₂ CF ₂ -O) _n -CF ₂ -CF ₂ - (n represents a repetition number).
Y ^a represents an acyloxy group or a halogen atom.
&Lt; / RTI >
???????? CH ₂ = CH-O-CH ₂ -PFPE-CH ₂ -O-CH = CH ₂ (wherein the symbols have the same meanings as defined above)
&Lt; / RTI >
Y ^a -H (wherein the symbols have the same meanings as defined above)
&Lt; / RTI > with a compound represented by formula < RTI ID = 0.0 >

37. The method according to any one of claims 34 to 36,
A compound represented by the formula: Y ^a -H is CF ₃ COOH.